DESC:Technical filed:
The present invention provides insecticidal and pesticidal compositions based on castor fatty acid. More particularly, the present invention provides an insecticidal and pesticidal compositions comprising castor fatty acidarginine salt in combination with at least one of coconut fatty acid, nonanoic acid, octanoic acid, oleic acid along with at least one adjuvant.

Background and prior art:
The fatty acid salts having from 8 to 20 carbon atoms are known to exhibit some insecticidal properties. Various fatty acid based pesticidal compositions are disclosed in US4774234; US4826678; US5093124; EP0617888 and WO2017042554. Although the salts of certain fatty acids are known to have insecticidal and miticidal properties the unsaturated C18 fatty acids are toxic to many soft bodied insects (EP0617888). However, the fatty acid salts having a carbon chain length below 12 are reported to be displayed phytotoxic properties (WO2017042554).

The factors which influence the effectiveness of such insecticides include the ability of the compound/composition to effectively spread on a target surface and the ability of the compound to penetrate the insect's cuticle thereby damaging the membrane and ultimately killing the pest.

Therefore, pesticides based on fatty acid salts are contact pesticides requiring direct application to the pests such as soft-bodied insects and mites to be effective.
These fatty acid salt compositions have low mammalian toxicity and are compatible with other forms of biological control such as semiochemicals, microbial pesticides, inorganic pesticides etc.

EP 0 617 888 A discloses an environmentally compatible composition toxic to insects and mites, which comprises; one or a mixture of fatty acids salts-having from 8 to 22 carbon atoms; and an adjuvant to increase the spread ability and efficacy of the fatty acid salt, the adjuvant selected from the group consisting of fatty alcohols having from 4 to 18 carbon atoms and fatty acid esters are selected from the group consisting of the methyl or ethyl esters of fatty acids having from 4 to 18 carbon atoms, the ratio of the adjuvant to the fatty acid salt being in the range of about 1 :0.1 to 1 :50. The fatty acid salt is a potassium, sodium, iron, calcium, copper, ammonium, or alkanolamine salt of monocarboxylic fatty acids having from 8 to 22 carbon atoms.

WO2017042554 discloses an insecticide or miticide composition which comprises: a fatty acid/amino acid salt, the fatty acid component comprising: one or more unsaturated fatty acids having from14 to 22 carbon atoms; and one or more saturated fatty acids having from 8 to 18 carbon atoms; wherein the one or more saturated fatty acids having from 8 to 18 carbon atoms forms at least 15 wt.% of the fatty acid component, and wherein the weight ratio of unsaturated fatty acids having from 14 to 22 carbon atoms to saturated fatty acids having from 8 to 18 carbon atoms is at least 1.The fattyacid/amino acid salt is selected from glycine, arginine or lysine or combination thereof.

Despite the known effectiveness of certain fatty acid-based compositions as pesticides, as discussed above, there is still a need for more environmentally-compatible compositions that can provide cost-effectiveness or enhanced efficacy or both, for the effective treatment of insects and pests.

Summary of the invention:
In accordance with the same, the present invention provides insecticidal and pesticidal compositions having low phytotoxicity based on castor fatty acid.

Accordingly, the insecticidal and pesticidal compositions comprising
a) castor fatty acid arginine salt in a concentration range of 15 to 40%;
b) at least one additional fatty acid in a concentration range of 10 to 25%; and
c) at least one adjuvant in a concentration range of 30 to 50%,
wherein, the pH of the formulations is in the range of 7.5 to 9.0.

According to the invention, the additional fatty acid is selected from coconut fatty acid, nonanoic acid, octanoic acid and oleicacid.

According to the present invention, the adjuvantis selected from C1 to C5 alcohols, viz. methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol and propylene glycol.

Accordingly, in an aspect, the invention provides insecticidal and pesticidal compositions comprising castor fatty acid arginine salt and coconut fatty acid.

In another aspect, invention provides insecticidal and pesticidal compositions comprising castor fatty acid arginine salt and nonanoic acid.

In another aspect, invention provides insecticidal and pesticidal compositions comprising castor fatty acid arginine salt and octanoic acid.

In another aspect, invention provides insecticidal and pesticidal compositions comprising castor fatty acid arginine salt and oleic acid.

In another aspect, invention provides insecticidal and pesticidal compositions based on saturated or unsaturated hydroxy fatty acids for example, ricinoleic acid with arginine and one of the following acids such as nonanoic/octanoic/oleic acid along with at least one adjuvant.

In another aspect, invention provides insecticidal and pesticidal compositions based on saturated or unsaturated dienoic fatty acids for example, linoleic acid with arginine and at least one fatty acid selected from the group consisting of nonanoic acid, octanoic acid and oleic acid along with at least one adjuvant.

According to the invention, the adjuvants are preferably selected from ethanol and n-Butanol.

Description of drawings:
Figure 1 depicts phytotoxicity studies conducted using 2% concentration of the formulations of FIPL/IN/FA-AG/7016 on cotton plants

Figure 2 depicts phytotoxicity studies conducted using 3% concentration of the formulations of FIPL/IN/FA-AG/7012 on tomato plants

Detailed description of the invention:
The invention will now be described in detail in connection with certain preferred and optional embodiments, so that various aspects thereof may be more fully understood and appreciated.

The present invention provides insecticidal and pesticidal compositions based on castor fatty acid.
Accordingly, the insecticidal and pesticidal compositions comprising
a) castor fatty acid arginine salt in a concentration range of 15 to 40%;
b) at least one additional fatty acid in a concentration range of 10 to 25%; and
c) at least one adjuvant in a concentration range of 30 to 50%,
wherein, the pH of the formulations is in the range of 7.5 to 9.0.

According to the invention, the additional fatty acid is selected from coconut fatty acid, nonanoic acid, octanoic acid, oleic acid.

According to the invention, the adjuvant is selected from C1 to C5 alcohols, viz. methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol andpropylene glycol.

Accordingly, in an embodiment, the invention provides insecticidal and pesticidal compositions comprising castor fatty acid and coconut fatty acid along with an adjuvant.

In another embodiment, the invention provides insecticidal and pesticidal compositions comprising castor fatty acid arginine salt and nonanoic acid, along with an adjuvant.

In yet another embodiment, the invention provides insecticidal and pesticidal compositions comprising castor fatty acid arginine salt and octanoic acid along with an adjuvant.

In another aspect, invention provides insecticidal and pesticidal compositions based on castor fatty acid arginine salt and oleic acid along with an adjuvant.

In an additional embodiment, invention provides insecticidal and pesticidal compositions based on saturated or unsaturated hydroxy fatty acids for example, ricinoleic acid with arginine and at least one fatty acid selected from the group consisting of nonanoic acid, octanoic acid and oleic acid along with at least one adjuvant.

In an additional embodiment, invention provides insecticidal and pesticidal compositions based on saturated or unsaturated dienoic fatty acids for example, linoleic acid with arginineand at least one fatty acid selected from the group consisting of nonanoic acid, octanoic acid and oleic acid along with at least one adjuvant.

Additionally, the amino acid component may also be selected from glycine, histidine, lysine, tryptophan, aspartic acid, glutamic acid, asparagine, cysteine, tyrosine, alanine, phenyl alanine, proline, valine, isoleucine, leucine, and methionine.
However, the preferred amino acid is arginine. According to the invention; the adjuvants are preferably selected from ethanol and n-butanol.

The preparation of fatty acid arginine salt reaction is carried out at a temperature range of 30-100 ºC preferably 30-70 ºC depending on the nature of fatty acids.

In another embodiment, these insecticidal and pesticidal compositions/formulations are effective against wide range of pests such as Fall army worm (Spondoptera frugiperda), Cotton thrips (Frankliniella schultzei), Cotton pink boll worm (Pectinophora gossypiella), Black bean aphids (Aphis fabae), Brown mite (Eutetranychus orientalis), Hibiscus mealybug (Maconellicoccu shirsutus), Whiteflies (Siphoninusphillyreae), Stink bug (Halyomorpha halys).

In another embodiment, the invention provides general procedure for the preparation of insecticidal and pesticidal compositions /formulations as detailed herein below.

Hydrolysis of Oil:
Hydrolysis of various oils were conducted by saponification using sodium hydroxide followed by neutralization using hydrochloric acid as described in AOAC official method 920.160, 20th edition (2016).

The resultant fatty acids were characterized using GC, HNMR and MS. GC chromatogram of castor fatty acid shows a mixture of fatty acid with ricinoleic acid (85%) as the major component and oleic acid (9%) as the minor components together with other fatty acids. 1HNMR: (500 MHz, CDCl3) d 0.88 (3H, d, J = 6.9 Hz), 1.29 (18H, t, J = 13.1 Hz), 1.47 (3H, d, J = 6.2 Hz), 1.63 (2H, s), 2.03 (2H, m), 2.21 (2H, t, J = 6.5 Hz), 2.34 (2H, s), 3.62 (1H, q, J = 5.5 Hz), 4.12 (2H, q, J = 7.3 Hz), 5.38 (1H, m), 5.56 (1H, m); MS: 297.2 (M-1) (Calcd MW: 298.48).

In another embodiment, the invention provides preparation of Fatty acid-Arginine salt, as described herein below.

Preparation of Fatty Acid-Arginine salt:
The acid value of coconut and castor acid were found to be 265 mg KOH/g of oil and 180.5 mg KOH/g of acid respectively (As per AOAC official method 969.170, 20th edition, 2016).

Required amount of castor fatty acids prepared from hydrolysis of castor oil was weighed and were taken into three necked round bottom flasks fitted with overhead stirrer and condenser. The mixing of castor fatty acids was done at temperature of 30-70 ºC depending on the nature of fatty acids. To the mixture of fatty acids, basic amino acid, preferably arginine was added and allowed to mix properly. Then base solution, preferably potassium hydroxide solution prepared using ethanol, propylene glycol and water was added to this mixture. In some formulations, n-butanol was used instead of ethanol as an adjuvant. The solid should be completely dissolved in base solution to become a homogeneous solution. Then heating was removed and the flask was allowed to cool down. The amount of solvents evaporated should be compensated by using either propylene glycol or n-butanol depending upon the nature of formulation. To these formulations, was added at least one additional fatty acid selected from coconut fatty acid, nonanoic acid, octanoic acid and oleic acid. The pH of these formulations were measured and found to be in the range of 7.5 to 9.0. The details of the formulations are provided under Table 1 (Example 1-9).

Table 1:
Example No. Code (FIPL/IN/FA-AG) Components used for the preparation of formulation (100 g) pH @ 29 ºC Density (g/ml) @ 30 ºC
1 (as per WO2017042554) 7010 Coconut Acid 14.49 Oleic Acid 22.03 Arginine 11.88 KOH 4.38 Butanol 20 Propylene Glycol 10 Water 17.22 8.14 0.95
2 7011 Castor Fatty Acid 21.21 Nonanoic Acid 12.34 Arginine 11.88 KOH 4.38 Butanol 20 Propylene Glycol 10 Water 20.19 8.01 0.98
3 7012 Castor Fatty Acid 21.21 Nonanoic Acid 12.34 Arginine 11.88 KOH 4.38 Ethanol 20 Propylene Glycol 10 Water 20.19 8.05 0.98
4 7013 Castor Fatty Acid 21.21 Octanoic Acid 11.25 Arginine 11.88 KOH 4.38 Butanol 20 Propylene Glycol 10 Water 21.28 7.77 0.96
Example No. Code (FIPL/IN/FA-AG) Components used for the preparation of formulation (100 g) pH @ 29 ºC Density (g/ml) @ 30 ºC
5 7014 Castor Fatty Acid 21.21 Octanoic Acid 11.25 Arginine 11.88 KOH 4.38 Ethanol 20 Propylene Glycol 10 Water 21.28 7.93 0.97
6 7015 Castor Fatty Acid 21.21 Oleic Acid 22.04 Arginine 11.88 KOH 4.38 Butanol 20 Propylene Glycol 10 Water 10.49 8.21 0.97
7 7016 Castor Fatty Acid 21.21 Oleic Acid 22.04 Arginine 11.88 KOH 4.38 Ethanol 20 Propylene Glycol 10 Water 10.49 8.17 0.95
8 7017 Castor Fatty Acid 24.27 Coconut Acid 14.49 Arginine 11.88 KOH 4.38 Butanol 20 Propylene Glycol 10 Water 14.98 7.85 0.96
9 7018 Castor Fatty Acid 24.27 Coconut Acid 14.49 Arginine 11.88 KOH 4.38 Ethanol 20 Propylene Glycol 10 Water 14.98 8.0 0.96

Example 10
The formulation FIPL/IN/FA-AG/7016 (Example 7) was prepared in 2.0 kg batch. The acid value of castor fatty acid was found to be 156.16 mg KOH/g of castor fatty acid. The formulation details are mentioned in Table 2.
Table 2:

Name of the Commodity Amount taken (g)
Castor Fatty Acid 491
Oleic Acid 441
Potassium Hydroxide 88
Arginine 238
Ethanol 400
Propylene Glycol 200
Water 142

Insecticidal Activity
Insecticidal effectiveness was carried out for Example 1 to 9 on the following insects
1. Fall Army Worm (Spondoptera frugiperda)
2. Cotton Pink boll worm (Pectinophora gossypiella)
3. Black bean aphids (Aphis fabae)
4. Hibiscus mealybug (Maconellicoccu shirsutus)

In another embodiment, the present inventors have conducted dose determination studies. According to the teachings of WO2017042554, fatty acid formulations may develop phytotoxicity at a concentration of above 2% (w/w) of fatty acid. WO2017042554 also states that if the fatty acid concentration is 1% (w/w) or below, these formulations may show reduced pesticidal properties.
In the light of the above and also from commercial point of view, the present inventors thought it was necessary to determine the lowest concentration at which these formulations are active and accordingly, the fatty acid formulations at three different concentrations viz., 0.5%; 0.75% and 1%w/w with respect to fatty acid concentration were chosen for entomological studies. The formulations viz example 1 to 9 was diluted with water to make desired concentrations. For all the studies surface topical application method was used. Delegate, a market control (recommended dose 1ml/L), was used for these studies. Delegate consists of Spinetoram, a chemical in the spinosyn class of insecticides.
Table 3:
Efficacy of Formulations at 0.5 % w/w Fatty Acid concentration after 48 hrs
Code (FIPL/IN/FA-AG) Efficacy on different pest
Fall Army Worm Cotton Pink Boll worm Black Bean Aphids Hibiscus Mealybug
7010 Excellent Excellent Excellent Excellent
7011 Excellent Excellent Good Minimal
7012 Excellent Very Good Very Good Minimal
7013 Minimal - Minimal Minimal
7014 Excellent Very Good Good Excellent
7015 Excellent Excellent Very Good Excellent
7016 Excellent Very Good Excellent Excellent
7017 Very Good - Minimal Excellent
7018 Excellent Excellent Good Excellent
Delegate (1ml/L) Excellent Excellent Excellent Excellent

Table 4:
Efficacy of Formulations at 0.75 % w/w Fatty Acid concentration after 48 hrs
Code (FIPL/IN/FA-AG) Efficacy on different pest
Fall Army Worm Cotton Pink Boll worm Black Bean Aphids Hibiscus Mealybug
7010 Excellent Excellent Excellent Excellent
7011 Excellent Excellent Excellent Minimal
7012 Excellent Very Good Excellent Minimal
7013 Minimal - Minimal Minimal
7014 Excellent Excellent Excellent Excellent
7015 Excellent Excellent Excellent Excellent
7016 Excellent Excellent Excellent Excellent
7017 Very Good - Minimal Excellent
7018 Excellent Excellent Excellent Excellent
Delegate (1ml/L) Excellent Excellent Excellent Excellent

Table 5:
Efficacy of Formulations at 1 % w/w Fatty Acid concentration after 48 hrs
Code (FIPL/IN/FA-AG) Efficacy on different pest
Fall Army Worm Hibiscus Mealybug
7010 Excellent Excellent
7011 Excellent Minimal
7012 Excellent Good
7013 Minimal Good
7014 Excellent Excellent
7015 Excellent Excellent
7016 Excellent Excellent
7017 Excellent Excellent
7018 Excellent Excellent
Delegate (1ml/L) Excellent Excellent

Note: Efficacy categories based on mortality rate; Minimal: 0% to 50% mortality: Good: 50% to 70% mortality: Very Good: 70% to 90% mortality: Excellent: 90%- to 100% mortality
When mortality rate of all the samples compared against FIPL/IN/FA-AG7010, FIPL/IN/FA-AG/7016 (Example 7) was found to be best one.
Further the activity of FIPL/IN/FA-AG/7016 was investigated on Brown marmorated stink bug (Halyomorpha halys) using surface topical application method. Excellent mortality rate was observed even at 0.25% w/w after 24 hrs.

Table 6:
Efficacy of Formulation FIPL/IN/FA-AG/7016on Brown Marmorated Stink Bug
Mortality Rate @ 24 hrs
Concentration % w/w
0.25 0.5 0.75
Excellent Excellent Excellent

Phytotoxicity Study:
The phytotoxicity was conducted according to the principles mentioned in OEPP/EPPO bulletin (2014) 44(3), 265-273 “PP 1/135 Phytotoxicity Assessment.” The study was conducted on four months old cotton plants. The formulations were diluted with water to make 2% w/w of fatty acid concentration. For the study healthy cotton plants were selected and the plants were completely drenched with solutions under testing. Visual assessment was carried out before spraying and 24, 48 and 72 hours of spraying. There were no visible traces of phytotoxicity recorded at 2% w/w on Cotton plants.
Phytotoxicity categories:
None: No sign of phytotoxicity; Slight: Traces of decolourization or scorching; Moderate: Significant decolourization or sign of scorching but less than 50% of leaf surface area; Severe: Curling of leaves with necrosis
Further phytotoxicity studies have been conducted using FIPL/IN/FA-AG 7011, 7012, 7013, 7014, 7015, 7016, 7017 and 7018 on Tomato and Brinjal (for both the plants, age was one month after transplanting) at 1%, 2% and 3% w/w of fatty acid concentrations. Like previous experiment on cotton, the plants were completely drenched with solutions under testing. Visual assessment was carried out before spraying and after 72 hours of spraying. There were no visible traces of phytotoxicity recorded even at 3% w/w on Tomato and Brinjal plants.

The observations from phytotoxicity studies conducted at 2% concentration (w/w) of fatty acids using formulations FIPL/IN/FA-AG/7016 on cotton plants and at 3% w/w concentration of fatty acid FIPL/IN/FA-AG/7012 on tomato plants are depicted in figure 1 and figure 2 respectively.

Inference could be drawn from these figures that no necrosis or chlorosis is observed at 2% w/w and 3% w/w fatty acid concentration on different plants having different age also and hence the present formulations are safe to administrate at 2%w/w and 3%w/w fatty acid concentration as this higher concentration does not show any phytotoxicity.
,CLAIMS:
1. Insecticidal and pesticidal compositions having low phytotoxicity comprising
a) castor fatty acid arginine salt in a concentration range of 15 to 40%;
b) at least one additional fatty acid in a concentration range of 10 to 25%; and
c) at least one adjuvant in a concentration range of 30 to 50%,
wherein, the pH of the formulations is in the range of 7.5 to 9.0.

2. The insecticidal and pesticidal compositions as claimed in claim 1, wherein the additional fatty acid is selected from coconut fatty acid, nonanoic acid, octanoic acid, oleic acid.

3. The insecticidal and pesticidal compositions as claimed in claim 1, wherein the adjuvant is selected from C1 to C5 alcohols, viz. methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol and propylene glycol.

4. The insecticidal and pesticidal compositions as claimed in claim 1, wherein the adjuvant is selected from methanol and n-Butanol.

5. The insecticidal and pesticidal compositions as claimed in claim 1, wherein the composition comprises castor fatty acid arginine salt and coconut fatty acid along with at least one adjuvant.

6. The insecticidal and pesticidal compositions as claimed in claim 1, wherein the composition comprises castor fatty acid arginine salt and nonanoic acid along with at least one adjuvant.

7. The insecticidal and pesticidal compositions as claimed in claim 1, wherein the composition comprises castor fatty acid arginine salt and octanoic acid along with at least one adjuvant.

8. The insecticidal and pesticidal compositions as claimed in claim 1, wherein the composition comprises castor fatty acid arginine salt and oleic acid along with at least one adjuvant.
9. An insecticidal and pesticidal compositions comprising ricinoleic acid with arginine and one of the fatty acids selected from the group consisting of nonanoic acid, octanoic acid and oleic acid along with at least one adjuvant.

10. An insecticidal and pesticidal compositions comprising linoleic acid with arginine and at least one of the fatty acid selected from the group consisting of nonanoic acid, octanoic acid and oleic acid along with at least one adjuvant.