Process for preparing .beta.' form of copper 8-hydroxyquinoline

A process for the preparation of the .beta.' form of the copper chelate of 8-hydroxyquinoline (copper oxinate), stabilized compositions containing said chelate, fungicidal compositions containing said chelate, and the methods for using said .beta.' form chelate or compositions for combatting fungi are disclosed.

SUMMARY OF THE INVENTION 
The invention relates to a process for preparing the .beta.' form of the 
copper chelate of 8-hydroxyquinoline. The .beta.' form is prepared by 
reacting a salt of 8-hydroxyquinoline with a copper (II) salt in water to 
produce the .beta. form of the chelate, treating the aqueous reaction 
mixture with base to adjust the pH to about 2-9, isolating the .beta. form 
and then drying the .beta. form at a temperature between 
40.degree.-220.degree. C. to yield the .beta.' form of the chelate. 
This invention also relates to stabilized compositions containing the 
.beta.' form of the copper chelate of 8-hydroxyquinoline, to fungicidal 
compositions containing said .beta.' form and to methods for the use of 
the .beta.' form in combatting fungi. 
BACKGROUND OF THE INVENTION 
It has been known that the chelate of copper (II) with 8-hydroxyquinoline, 
hereinafter referred to as copper oxinate, possesses biocidal properties 
and is useful as a fungicide in the treatment of cereal seeds and is also 
suitable for protecting plants. The advantages of copper oxinate include 
being non-irritating, possessing very low toxicity, almost zero 
volatility, high stability and can be prepared without any ecological 
problems. 
The copper oxinate currently marketed possesses valuable activity against 
fusarium diseases, glume blotch and bunt; however, its activity against 
leaf stripe of barley is rather low. It is one of the objects of the 
present invention to find a compound possessing all the advantages of 
copper oxinate, but also possessing a broad activity spectrum with a high 
level of efficacy. 
It has also been known that copper oxinate is a polymorphous compound, i.e. 
it has various crystalline forms, see Palenik, Acta. Cryst., 1964, 17(6), 
687-695 and Suito, et al., Kolloid-z.z. Polym., 1966, 212(2), 155-161. 
Seven crystalline forms of copper oxinate have been reported, namely 
.alpha., .alpha.', .beta., .beta.', .beta.", .gamma. and .gamma.' forms. 
The .alpha., .alpha.', .gamma. and .gamma.' forms are considered as 
laboratory curiosities, while the .beta. form is the most stable under 
normal conditions in which copper oxinate is used. 
It has been found that the .beta.' form of copper oxinate, considered to be 
unstable and to be a transition form between the .beta. form, which is 
stable under normal conditions, and the .beta." form, which is stable at 
higher temperatures, in fact possesses a broader activity spectrum than 
the .beta. form and exhibits enhanced efficacy as an antifungal agent. 
DETAILED DESCRIPTION OF THE INVENTION 
The present invention relates to a process for preparation of the .beta.' 
form of the copper chelate of 8-hydroxyquinoline (i.e. copper oxinate). 
The process of the present invention for preparing the .beta.' form of 
copper oxinate comprises: 
(a) reacting a salt of 8-hydroxyquinoline and a copper (II) salt in water; 
(b) adding a base until the pH of the reaction is between 2 and 9; 
(c) recovering the precipitate of the .beta. form of copper oxinate and 
(d) drying the .beta. form of copper oxinate at a temperature between about 
40.degree. C. and about 220.degree. C. to yield the .beta.' form of copper 
oxinate. 
Copper oxinate in the .beta.' form has a molecular formula (C.sub.9 H.sub.6 
ON).sub.2 Cu and is in the form of a strongly electrostatic, olive-green 
solid having a filamentous microstructure. The principal X-ray diffraction 
lines in decimal degrees are: (2.theta.)=7.15; 11.95; 13; 14.7. 
In contrast to the vast majority of organic compounds which can be obtained 
as pure species by physical purification methods, the physicochemical 
characteristics of oxine chelates (8-hydroxyquinoline chelates) and 
particularly the copper (II) oxine chelate are completely determined by 
the quality of each of the starting materials used, by the composition of 
the reactants, and by the conditions under which the reaction is carried 
out, including those relating to washing and drying. 
In carrying out the process of this invention, step (a) is conducted in an 
aqueous phase, preferably an aqueous solution of an oxine salt (i.e. salt 
of 8-hydroxyquinoline) is reacted with an aqueous solution of a copper 
(II) salt. It is preferable to carry out this reaction utilizing a slight 
stoichiometric excess of the oxine salt, for example, less than 5 mol 
percent. 
The preferred oxine salt for this reaction is oxine sulfate; however, other 
acid addition salts of oxine can be utilized, for example, the nitrate and 
the phosphate. 
The preferred copper (II) salt is copper (II) sulfate; however, other 
copper (II) salts can be utilized, for example, the nitrate and the 
phosphate. 
The reaction of the oxine salt and the copper (II) salt is carried out at a 
temperature below 40.degree. C. and preferably between 0.degree. C. and 
20.degree. C., for example, about 10.degree. C. 
The acidity resulting from the reaction in step (a) is neutralized in situ 
by addition of a base. The addition of base is carried out at the same 
temperature as step (a). Examples of bases which can be employed in the 
process include ammonia, alkali metal or alkaline earth metal hydroxides, 
or organic amines. The preferred base is ammonia. 
The pH at the end of the reaction is critical because, by adjusting the 
latter within the range of 2.0-3.5, preferably with the range 2.5-2.8, it 
is possible to free the reaction mixture not only of the oxime resulting 
from the neutralization of the excess 8-hydroxyquinoline salt, but also 
the major part of the oxinates of the other metals which are inevitably 
present in the reactants, for example Fe, Ni, Ca and Mg. 
The drying step (d) is carried out at temperatures between 40.degree. and 
220.degree. C., and preferably between 60.degree. and 160.degree. C. In 
the latter temperature range, the time period for drying the product will 
vary between 0.5 second to 120 minutes. If the drying temperature is in 
the range of 80.degree. to 140.degree. C., the time of drying will be from 
0.5 second to 20 minutes. It is understood that the higher the 
temperature, the shorter the drying time. It should be noted that if the 
.beta.' form is kept at a high temperature too long, it is converted to 
the .beta." form, which is further converted to the stable .beta. form at 
ambient temperatures. In fact, over a period of 275 hours at 30.degree. 
C., 80% of the .beta." polymorph is converted to the .beta. form in the 
presence of water. 
The copper oxinate in the .beta.' form prepared according to the process of 
this invention contains less than 1% of impurities, which makes it a 
particularly valuable product for the protection of plants. 
As noted above, copper oxinate in the .beta.' form is readily converted to 
the .beta. form in the presence of water. In the majority of applications, 
copper oxinate is used in an aqueous medium, for example, in the form of 
concentrated or dilute aqueous mixtures and, therefore, the use of the 
.beta.' form in such mixtures would lead to rapid conversion to the .beta. 
form. 
For practical use of copper oxinate in the .beta.' form, it is, therefore, 
necessary to have available stabilized compositions, for example, wettable 
powders or aqueous suspensions, which can be stored without conversion to 
the .beta. form and which can be diluted in water at least 24 hours before 
use, without loss of activity of the product. 
Another aspect of the present invention relates to stabilized compositions 
comprising copper oxinate in the .beta.' form, as the active ingredient, 
and an agent for inhibiting the hydration of the copper oxinate in the 
.beta.' form. 
Examples of agents for inhibiting hydration of copper oxinate in the 
.beta.' form include low molecular weight phenoplast-type polycondensates 
of cresol and formaldehyde, polycondensates of alkylnaphthalenesulfonic 
acids with formaldehyde, commonly referred to as 
polyalkylnaphthylmethanesulfonics, and their salts, arenesulfonic acids, 
for example, benzenesulfonic acid, toluenesulfonic acid, 
naphthalenesulfonic acid and their salts, polyacrylic acids, their 
homologoues and their salts, and lignosulfonic acid and lignosulfonates. 
In addition to their stabilizing properties, the foregoing materials are 
dispersing surfactants. 
In addition to their inherent physicochemical properties, the stabilizers 
are characterized by the buffering capacity which they impart to the 
solution, and the presence in their molecules of functional groups, 
especially OH and/or NH.sub.2 and/or SO.sub.3 H groups. These functional 
groups are capable of forming a bond of low energy with the copper atom. 
The following substances are particularly effective hydration inhibitors: 
8-hydroxyquinoline-5-sulfonic acid (sulphoxine) and its salts, and halogen 
substituted sulphoxines, preferably 7-iodo-8-hydroxyquinoline-5-sulfonic 
acid and its salts. 
Other materials which can be employed in the compositions of the present 
invention include polyvinyl alcohol, alkylcelluloses and 
hydroxyalkylcelluloses, carboxyalkylcelluloses, polyvinylpyrrolidone, 
polyacrylamides, carbohydrates, such as starches, hemicelluloses and gums, 
and polypeptides, in particular casein and caseinates, including powdered 
milk. These materials impart adhesion to spraying compositions and also 
have a pronounced stabilizing action and partially inhibit the hydration 
of the .beta.' form. 
The concentration of stabilizer in the compositions of this invention 
depends on the nature of the stabilizer and also varies as a function of 
the nature of the composition. In general, the stabilizer will be present 
in the composition in the range of from about 0.1 percent by weight to 
about 20 percent by weight. 
It should be pointed out that copper oxinate is both a brittle and friable 
material. Therefore, in order to obtain uniform particles having a size 
which is at the limit of detection of an optical microscope, i.e. in the 
region of 10.sup.-4 or 10.sup.-5 cm, it is necessary to employ percussion 
and attrition methods of fragmentation. To obtain the desired particle 
size, any type of ultramicronization grinder, for example, jet micronizers 
(air or steam jets) can be used. Preferably, ball grinders or bead mills 
operating along a horizontal or vertical axis are employed. The procedure 
is carried out on an aqueous suspension having an oxinate concentration 
between about 1 and 80% by weight, preferably between 20 and 50% by 
weight. A colloidal solution containing copper oxinate particles in the 
appropriate size range can be prepared using beads having a diameter of 
1.5 mm as the grinding bodies. During the grinding procedure, all the 
necessary adjuvants are added to impart stability to the allotrope in 
question, to assist the micronization or to impart, to the suspension, the 
optimum characteristics suited to the type of application contemplated. 
This invention is also directed to fungicidal compositions useful in 
combatting fungi of plants and especially seeds. The fungicidal 
compositions comprise a compatible carrier material and, as the active 
ingredient, copper oxinate in the .beta.' form. These compositions can be, 
for example, spray liquors, aqueous suspension, and emulsions. They may 
contain from about 5-20% by weight of .beta.' copper oxinate and from 
about 0.5-5% of hydration inhibitor, the rest to 100% being carrier 
material. 
Examples of compatible carrier materials include pulverous materials, such 
as, for example, kaolin, chalk, bentonite, talc, whiting, magnesium 
carbonate and siliceous earth. The compositions may also contain wetting 
agents, inert diluents, solvents, dispersing agents and stabilizers. 
Representative examples of the inventive fungicidal compositions are the 
following: 
Compositions for treating the aerial parts of plants, which can be applied 
in the form of dilute aqueous sprays: 
______________________________________ 
Ingredient 
______________________________________ 
I. 
copper oxinate, .beta.' form 
50% 
sodium polynaphthylmethanesulfonate 
2% 
sodium lignosulfonate 3% 
sulphoxine(8-hydroxyquinoline-5-sulfonic acid) 
1% 
chalk 19% 
kaolin 25% 
II. 
copper oxinate, .beta.' form 
400 g 
sodium polynaphthylmethanesulfonate 
15 g 
sodium lignosulfonate 25 g 
sulphoxine 10 g 
ethylene glycol 50 g 
colloidal silica 25 g 
silicone anti-foam agent 2 g 
polysaccharide 2 g 
water, q.s.p. 1 liter 
______________________________________ 
The antifungal treatment of seeds may also be combined with protection 
against insects of the soil as well as bird repellant agents. Lindane is 
an example of an insecticide which can be employed, and anthraquinone is 
an example of a bird repellant that may be employed. 
An example of a triple composition for treating seeds which can be used in 
the form of a concentrated aqueous spray is: 
______________________________________ 
Ingredient 
______________________________________ 
copper oxinate, .beta.' form 
15% 
lindane 25% 
anthraquinone 25% 
sodium polynaphthylmethanesulfonate 
1% 
sulphoxine 0.2% 
kaolin 14.8% 
chalk 10% 
polyvinyl alcohol 5% 
red 53-1* 4% 
______________________________________ 
*[(4-Hydroxy-1-naphthalenyl)azo]-4'-chloro-5'-methyl-benzene-sulfonic aci 
barium salt. 
The copper oxinate in the .beta.' form can also be used in the protection 
of animal feeds and leather, in the protection of cellulose materials, 
such as paper pulp, wood, paint, glue and fabrics, and also for the 
protection of hydrocarbons.

The following Examples illustrate the present invention. 
EXAMPLE 1 
Preparation of the .beta. polymorph: (C.sub.9 H.sub.6 ON).sub.2 
Cu.2(OH.sub.2) 
A solution prepared from 232.11 g (0.5688 mol+0.5%) of oxine sulfate and 
1,000 ml of water is added, over a period of 30 minutes and with vigorous 
stirring, to a solution, kept at 10.degree. C., consisting of 142 g 
(0.5688 mol) of copper sulfate pentahydrate and 1,200 ml of water. The 
copper oxinate, which has a delicate green color, appears from the 
introduction of the first drop of reactant, and the polymorphic conversion 
.alpha..fwdarw..gamma..fwdarw..beta. can be followed by examination under 
a microscope. 
The reactants mix without heat being evolved. While maintaining the initial 
temperature, 85% of the theoretical amount of ammonia (170 ml, d.sub.20/4 
=0.924) is introduced dropwise and then, following the pH, the 
neutralization is continued until the pH is between 2.5 and 
2.8(.perspectiveto.10 ml). The temperature is allowed to rise until it 
reaches ambient temperature, with gentle stirring. The chelate, which is 
in the form of hexagonal 20.mu. lamallae, is filtered off, washed with 
water (350 ml), drained and left to dry in the open air or using a 
suitably adjusted fluidized bed apparatus. This yields 250 g of moist 
product and 219.12 g (yield: 99.4%) of dry product having the following 
characteristics: 
% of (C.sub.9 H.sub.6 ON).sub.2 Cu=90.45; % of H.sub.2 O=9.45; total 
content of impurities (other metal oxinates, ammonium sulfate, oxine and 
water); .ltoreq.0.40%; polymorphic purity by X-ray diffraction: 100%; 
position of the principal X-ray diffraction lines in decimal degrees: 
(2.theta.)=6.95; 15.75; 16.00. 
Before being discarded, the mixture of the mother liquors and the wash 
liquors (3 liters) is neutralized to pH 7-8 (.perspectiveto.50 ml) and 
then allowed to stand for 12 hours. The precipitate, which consists mainly 
of iron oxinate, that is to say about 0.450 g, cannot easily be removed by 
filtration, but is more conveniently removed by centrifugation. 
EXAMPLE 2 
Preparation of the .beta.' polymorph: (C.sub.9 H.sub.6 ON).sub.2 Cu 
The process of drying the moist .beta. polymorph of copper oxinate involves 
the following two successive steps: 
(I) moist .beta.-oxinate.fwdarw..beta.-oxinate+moisture; 
(II) .beta.-oxinate.fwdarw..beta.'-oxinate+2(OH.sub.2). 
The drying operation (I) can be carried out in the open air or by means of 
a fluidized bed dryer. In a fluidized bed dryer, the air inlet temperature 
of which is adjusted to 40.degree. C., the moisture is completely removed 
in 10 minutes, whereas the degree of conversion in the second step is 
imperceptible. In fact, to take place in the reasonable period of 10 
minutes, the latter requires a temperature of 85.degree. C. 
The process can also be carried out by continuously spraying the dry copper 
oxinate in the .beta. form into a stream of hot air, the oxinate being 
heated to a temperature of 135.degree.-145.degree. C. for a period of the 
order of a second. 
As regards the polymorphic purity, the results commonly obtained are: 
.beta.: undetectable; .beta.": .ltoreq.1%. The strongly electrostatic, 
olive-green solid has a filamentous microstructure under a scanning 
electron microscope. 
Position of the principal X-ray diffraction lines in decimal degrees: 
(2.theta.)=7.15; 11.95; 13; 14.7. 
EXAMPLE 3 
The Example demonstrates the influence of a stabilizer on the preservation 
of copper oxinate in the .beta.' form at ambient temperature and at 
60.degree. C. The following compositions were prepared and used in the 
form of aqueous suspensions containing 5% by weight of copper oxinate in 
the .beta.' form. 
Composition A 
Copper oxinate in the .beta.' form, containing 1% by weight of sulphoxine 
(8-hydroxyquinoline-5-sulfonic acid in the free form or in the form of the 
Na salt). 
Composition B 
Copper oxinate in the .beta.' form, containing 10% by weight of the Na 
lignosulfonate. 
Composition C 
Copper oxinate in the .beta.' form, containing 5% by weight of polyoxyether 
of tridecyl alcohol (unstabilized composition). 
______________________________________ 
Percentage conversion to the .beta. form 
at ambient temperature 
0 h 2 h 6 
Time 15 m 1 h 30 m 7 h 20 h 90 h 190 h 
months 
______________________________________ 
Aqueous 4 22 52 92 100 
suspension 
containing 
5% of copper 
oxinate in the 
.beta.' form 
Composition A 
0 0 
Composition B 
0 0 
Composition C 92 
______________________________________ 
______________________________________ 
Percentage conversion to the 
.beta. form at 60.degree. C. 
Time 0 h 15 m 1 h 2 h 30 
7 h 
______________________________________ 
Aqueous suspension 
0 100 
containing 5% of 
copper oxinate in 
the .beta.' form 
Composition A 0 0 0 
______________________________________ 
These results indicate that the addition of a stabilizer considerably 
increases the ability of preserving copper oxinate in the .beta.' form, in 
aqueous suspension, whereas the addition of a conventional wetting agent 
considerably accelerates the conversion to the .beta. form. 
The following Examples compare the activity of copper oxinate in the .beta. 
and .beta.' form in the protection of seeds. The test procedures employed 
are in accordance with those prescribed by the Commission des Essais 
Biologiques de la Societe Francaise de Phytiatrie et de Phytopharmacie. 
EXAMPLE 4 
This Example compares the activity of the .beta. and .beta.' polymorphs 
against snow mould, glume blotch and bunt. 
The following compositions were prepared: 
______________________________________ 
Composition D Percentage by weight 
______________________________________ 
Copper oxinate, .beta. form 
16.60 
Polyethoxy ether of tridecyl alcohol 
0.75 
Chalk 29.20 
Kaolin 53.45 
______________________________________ 
______________________________________ 
Composition E Percentage by weight 
______________________________________ 
Copper oxinate, .beta.' form 
15.00 
Polyethoxy ether of tridecyl alcohol 
0.75 
Chalk 29.20 
Kaolin 55.05 
______________________________________ 
The compositions were used at a dose equivalent to 30 g/qunital of copper 
oxinate, expressed as (C.sub.9 H.sub.6 NO).sub.2 Cu. The seeds were 
treated immediately after preparation of the spraying composition. 
The results observed in the protection of the seeds against these diseases 
are reported in Table I. 
TABLE I 
______________________________________ 
ACTIVITY OF .beta. AND .beta.' COPPER OXINATE ON 
SNOW MOULD, GLUME BLOTCH AND BUNT 
______________________________________ 
Percentage of healthy plantlets 
Nature of the experiment 
OPEN 
SEED CUPS FIELD 
Disease 
Snow.sup.(1) 
Glume.sup.(2) 
mould blotch Bunt.sup.(3) 
Day of counting 
Composition S + 53 S + 83 Harvesting 
______________________________________ 
Composition D 
74 25 92.8 
Composition E 
85 68.5 97 
Untreated control 
48 6 49.3 
______________________________________ 
.sup.(1) Rye contaminated to the extent of 32% by Fusarium nivale 
.sup.(2) Clement wheat contaminated to the extent of 81% by Septoria 
nodorum 
.sup.(3) Clement wheat artificially contaminated to the extent of 
3.permill. by bunt 
The activity of .beta.' form is much greater than that of the .beta. form. 
EXAMPLE 5 
This Example illustrates the effect of a stabilizer on the activity of the 
.beta. and .beta.' polymorphs of copper oxinate against snow mould, glume 
blotch, bunt and leaf stripe of barley after 24 hours and in the presence 
of water. 
The following compositions were prepared: 
Composition G 
Copper oxinate, .beta. form, at a concentration of 5.55% by weight/volume 
in water. 
Composition H 
Copper oxinate, .beta.' form, at a concentration of 5% by weight/volume in 
water. 
______________________________________ 
Composition I 
______________________________________ 
Copper oxinate, .beta.' form 
5 g 
Na-lignosulfonate 0.5 g 
Water, q.s.p. 100 ml 
______________________________________ 
The compositions were used at a dose equivalent to 30 g/quintal of copper 
oxinate, expressed as (C.sub.9 H.sub.6 NO).sub.2 Cu. Unless indicated 
otherwise, the treatment of the seeds immediately followed the preparation 
of the spraying mixture. The results observed in the protection of the 
seeds against these diseases are reported in Table II. 
TABLE II 
______________________________________ 
EFFECT OF STABLIZER ON THE ACTIVITY OF .beta. AND 
.beta.' COPPER OXINATE AGAlNST SNOW MOULD, GLUME 
BLOTCH, BUNT AND LEAF STRIPE 
______________________________________ 
Percentage of healthy plantlets 
Nature of the experiment 
SEED CUPS OPEN FIELD 
Disease 
Snow.sup.(1) 
Glume.sup.(2) Leaf.sup.(4) 
Mould Blotch Bunt.sup.(3) 
Stripe 
Day of counting 
Harvest- 
Composition S + 23 S + 55 ing Earing 
______________________________________ 
Composition G 69.3 14.7 94.9 80.4 
Composition H 82 81.3 99.6 97.8 
Composition H after 24 h 
75.3 40 -- -- 
Composition I 80 78.3 98.9 98.8 
Composition I after 24 h 
82.7 76.7 99.6 99.1 
Untreated control 
63.3 5.3 80.6 63.6 
______________________________________ 
.sup.(1) Rye contaminated to the extent of 26% by Fusarium nivale 
.sup.(2) Talent wheat contaminated to the extent of 75% by Septoria 
nodorum 
.sup.(3) Clement wheat artificially contaminated to the extent of 
3.permill. by bunt 
.sup.(4) Astrix winter barley contaminated to the extent of 56% by 
Helminthosporium gramineum 
It is clearly apparent from Table II that the unstabilized aqueous 
compositions containing copper oxinate in the .beta.' form lose a large 
part of their activity after 24 hours, whereas the stabilized compositions 
retain a virtually unchanged activity. 
EXAMPLE 6 
This Example illustrates the efficacy of copper oxinate in the .beta.' form 
in the presence or absence of a stabilizer and in formulations containing 
other ingredients. 
The following compositions were prepared: 
______________________________________ 
Percentage by weight 
______________________________________ 
Composition D 
Copper oxinate, .beta. form 
16.60 
Polyethoxy ether of tridecyl alcohol 
0.75 
Chalk 29.20 
Kaolin 53.45 
Composition E 
Copper oxinate, .beta.' form 
15.00 
Polyethoxy ether of tridecyl alcohol 
0.75 
Chalk 29.20 
Kaolin 55.05 
Composition J 
Copper oxinate, .beta.' form 
15.00 
Sodium polynaphthylmethanesulfonate 
1.00 
Sulphoxine 0.2 
Chalk 29.2 
Kaolin 54.6 
______________________________________ 
The compositions were used at a dose equivalent to 30 g/quintal of copper 
oxinate, expressed as (C.sub.9 H.sub.6 NO).sub.2 Cu. Unless indicated 
otherwise, the treatment of the seeds immediately followed the preparation 
of the spraying mixture. 
The results observed in the protection of the seeds against leaf spot are 
reported in Table III. 
TABLE III 
______________________________________ 
EFFECT OF STABILIZER ON THE ACTIVITY OF .beta. AND 
.beta.' FORM OF COPPER OXINATE ON GLUME BLOTCH 
Percentage of healthy plantlets 
NATURE OF EXPERIMENT 
DISHES 
Disease 
Composition Leaf spot.sup.(1) 
______________________________________ 
Composition D 69.8 
Composition E after 24 hours 
65.3 
Composition J after 24 hours 
91.6 
Untreated control 9.8 
______________________________________ 
.sup.(1) Talent wheat contaminated to the extent of 90% by Septoria 
nodorum 
The results of Table III confirm the efficacy of the stabilizer as regards 
the .beta.' polymorph. 
EXAMPLE 7 
This Example illustrates the efficacy of copper oxinate in the .beta.' form 
in formulations containing other active ingredients, for example, 
insecticides and bird repellants. 
The following compositions were prepared: 
______________________________________ 
Composition K Grams/liter 
______________________________________ 
Copper oxinate, .beta. form 
133.3 
Lindane 200 
Anthraquinone 200 
Polyethoxy ether of tridecyl alcohol 
10 
Polyethoxy ether of nonylphenol 
15 
Red 53-1* 35 
Ethylene glycol 50 
Water, q.s.p to 1 liter 
______________________________________ 
______________________________________ 
Composition L Gram/liter 
______________________________________ 
Copper oxinate, .beta.' form 
120 
Lindane 200 
Anthraquinone 200 
Red 53-1* 35 
Sulphoxine 10 
Sodium polynaphthylmethanesulfonate 
20 
Polyvinyl alcohol 50 
Ethylene glycol 50 
Water, q.s.p. to 1 liter 
______________________________________ 
*[(4-Hydroxy-1-naphthalenyl)azo]-4'-chloro-5'-methyl-benzene-sulfonic aci 
barium salt. 
The compositions were used at a dose equivalent to 30 g/quintal of copper 
oxinate, expressed as (C.sub.9 H.sub.6 NO).sub.2 Cu. Unless indicated 
otherwise, the seeds were treated immediately following preparation of the 
spray mixture. 
The results observed in the protection of the seeds against glume blotch 
are reported in Table IV. 
TABLE IV 
______________________________________ 
EFFECT OF A STABILIZER ON THE ACTIVITY OF .beta. AND 
.beta.' FORMS OF COPPER OXINATE ON GLUME BLOTCH 
IN FORMULATIONS CONTAINING OTHER ACTIVE 
INGREDIENTS 
Percentage of healthy plantlets 
SEED CUPS 
NATURE OF EXPERIMENT 
Disease 
Composition Glume Blotch.sup.(1) 
______________________________________ 
Composition K 40.4 
Composition L after 24 hours 
81.2 
Untreated control 
9.5 
______________________________________ 
.sup.(1) Talent wheat contaminated to the extent of 90% by Septoria 
nodorum 
The results of Table IV confirm the efficacy of the stabilizer as regards 
the .beta.' polymorph in formulations containing other active ingredients.