# US 9,775,340 B2 · Biologically active formulation

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- Number: US 9,775,340 B2
- Document ID: US9775340B2
- Status: Granted
- Kind: B2
- Application number: 11/912,136
- Filed: 2006-04-21
- Published: 2009-05-21
- Granted: 2017-10-03
- Earliest claimed: 2005-04-22
- Assignees: Endura S.p.A.
- Applicants: Oreste Piccolo; Valerio Borzatta; Giovanna Delogu; Elisa Capparella; Cristina de Candia; Carlotta Gobbi; Giovanna di Blasi
- Inventors: Oreste Piccolo; Valerio Borzatta; Giovanna Delogu; Elisa Capparella; Cristina de Candia; Carlotta Gobbi; Giovanna di Blasi
- Web page: https://patentgrep.com/patent/US9775340B2

## CPC

- A01N 25/10: Macromolecular compounds
- A01N: PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF (preservation of food or foodstuff A23); BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES (preparations for medical, dental or toiletry purposes which kill or prevent the growth or proliferation of unwanted organisms A61K); PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS

## Abstract

The present invention provides a formulation characterized by the simultaneous presence in cyclodextrin based supramolecular complexes, of two components, one of which possesses insecticidal, acaricidal, fungicidal, snailcidal or vermicidal activity and the other possesses an activity synergistic with the first, enhancing its effectiveness. The biologically active substance is chosen from the following classes of chemical products: carbamates, organophosphates, thioureas, pentatomic or hexatomic heterocycles in which 1, 2 or 3 nitrogen atoms are present. The synergistic substance can be chosen from components containing at least one aromatic or non aromatic carbocyclic ring, such as piperonyl butoxide, sesamol, verbutin or MGK 264. For the same dose, the activity of the present formulations is greater than that of the mixture of the two active components alone or separately complexed with cyclodextrin. The process for preparing said formulation and its use for the activities herein indicated are further aspects of the present invention.

## Claims

### Claim 1

Supramolecular complex in a cyclodextrin comprising:
(i) an active principle with insecticidal, acaricidal, fungicidal, snailcidal or vermicidal activity which is selected from the group consisting of pirimicarb, fenazaquin, thiabendazole, pyrimethanil and diazinon, or a neonicotinoid selected from the group consisting of Imidacloprid, Acetamiprid;
(ii) a synergistic component that is able to synergistically enhance the activity of the active principle (i) selected from the group consisting of piperonyl butoxide, and verbutin; and
(iii) a cyclodextrin,
wherein when the synergistic component (ii) is PBO, then the active principle (i) is selected from the group consisting of fenazaquin, thiabendazole, pyrimethanil, diazinon, imidacloprid and acetamiprid; and
when the synergistic component (ii) is verbutin, then the active principle (i) is selected from the group consisting of pirimicarb, fenazaquin and imidacloprid.

### Claim 2 (depends on 1)

Complex as claimed in claim 1, wherein the cyclodextrin is selected from the group consisting of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin and a hydroxypropyl derivative of β-cyclodextrin.

### Claim 3 (depends on 1)

Complex as claimed in claim 1, wherein the quantity of active principle (i) relative to cyclodextrin is between 1% and 50% (weight/weight).

### Claim 4 (depends on 1)

Complex as claimed in claim 1, wherein the quantity of active principle (i) relative to cyclodextrin is between 2% and 30% (weight/weight).

### Claim 5 (depends on 1)

Complex as claimed in claim 1, wherein the quantity of synergistic component (ii) relative to cyclodextrin is between 0.1% and 100% (weight/weight).

### Claim 6 (depends on 1)

Complex as claimed in claim 1, wherein the quantity of synergistic component (ii) relative to cyclodextrin is between 20% and 70% (weight/weight).

### Claim 7 (depends on 1)

Complex as claimed in claim 1, wherein the quantity of active principle relative to the synergistic compound is between 0.5% and 7000% (weight/weight).

### Claim 8 (depends on 1)

Complex as claimed in claim 1, wherein the quantity of active principle relative to the synergistic compound is between 1% and 1500% (weight/weight).

### Claim 9 (depends on 1)

Complex as claimed in claim 1, wherein the quantity of active principle relative to the synergistic compound is between 10% and 70% (weight/weight).

### Claim 10 (depends on 1)

Composition with insecticidal, acaricidal, fungicidal, snailcidal or vermicidal activity comprising the supramolecular complex described in claim 1, in combination with a suitable additive and/or carrier.

### Claim 11 (depends on 10)

Composition as claimed in claim 10, further comprising an additional synergistic component in free or microemulsified form, wherein the additional synergistic component is the same as or different from the synergistic component present in the supramolecular complex with cyclodextrin.

### Claim 12 (depends on 11)

Composition as claimed in claim 11, wherein the quantity of synergistic component in free or microemulsified form is between 0% and 300% (weight/weight).

### Claim 13 (depends on 10)

Composition as claimed in claim 10, wherein said composition is formulated as a solid or as a solid/oil composition.

### Claim 14 (depends on 1)

Process for preparing the supramolecular complex described in claim 1, comprising the following steps:
(a) preparing a solution or suspension, in a suitable solvent, of the synergistic component (ii) and the active principle (i), optionally in the presence of a suitable surfactant;
(b) preparing a solution of cyclodextrin in water or in water/water-miscible organic solvent mixtures;
(c) adding the solution/suspension obtained in (a) to the solution obtained in (b); and
(d) maintaining the mixture obtained in (c) under stirring at a temperature between 40° and 90° C. for a time period between 12 and 36 hours.

### Claim 15 (depends on 14)

Process as claimed in claim 14, wherein:
in step (a) the surfactant is present in a quantity up to 12% by weight relative to the synergistic component, and the solvent is an alcoholic solvent
in step (b), dissolving the cyclodextrin is facilitated by heating to between 50° C. and 90° C. for 30-90 minutes;
in step (c) the solution/suspension of (a) is added over 2-10 hours, pre-heated to a temperature between 50° and 90° C.; and
in step (d) the mixture is maintained under stirring, at a temperature between 50° and 75° C. for a period between 18 and 24 hours.

### Claim 16 (depends on 14)

Process as claimed in claim 14, wherein the surfactant is present in a quantity between 2% and 4% by weight relative to the synergistic compound, and the solution or suspension in (a) is prepared in ethanol or isopropanol.

### Claim 17 (depends on 1)

Process for preparing the supramolecular complex described in claim 1, comprising the following steps:
(a) dissolving the active principle (i) in the synergistic compound (ii), heating the mixture;
(b) preparing a suspension of cyclodextrin in water and heating the suspension to a temperature between 60° and 80° C.;
(c) adding the heated solution obtained in (a) to the heated suspension obtained in (b); and
(d) maintaining the mixture obtained in (c) under stirring at a temperature between 50° and 90° C. for a time period between 1 and 12 hours.

### Claim 18 (depends on 17)

Process as claimed in claim 17 wherein:
in step (a) the active principle (i) is dissolved in the synergistic component (ii) at a temperature between 70° and 140° C. in the presence of a suitable surfactant in a quantity up to 12% by weight relative to the synergistic component (ii);
in step (b) the weight/weight percentage of cyclodextrin in water is between 30% and 70%;
in step (c) the solution of (a) is added over a period between 10 and 600 minutes;
in step (d) the mixture is maintained under stirring at a temperature between 70° and 90° C. for a period between 1 and 4 hours.

### Claim 19 (depends on 1)

Method for the eradication of insects, mites, moulds, molluscs or worms comprising treating a substrate requiring treatment with the supramolecular complex described in claim 1.

### Claim 20 (depends on 10)

Method for the eradication of insects, mites, molds, molluscs or worms characterised by treating a substrate requiring treatment with the composition described in claim 10.