BIO PESTICIDAL COMPOSITION CONTAINS NOVEL NONANOATE ESTERS OF SUGARS AND SUGAR ALCOHOLS TO CONTROL LEPIDOPTERA, HEMIPTERA AND THYSANOPTERA INSECTS

Abstract

The present invention discloses bio-pesticidal composition comprising novel nonanoate esters of sugar or sugar alcohol possessing pesticidal (insecticidal, arachnicidal, molluscicides, microbicidal etc) and herbicidal properties and their potential use in controlling Lepidoptera, Hemiptera and Thysanoptera insects. The present invention further discloses preparation of novel nonanoate esters of sugar or sugar alcohol and their formulations.

Claims

1. Bio pesticidal composition comprising nonanoate esters of sugars and sugar alcohols derived from C3 to C8 carbon atoms along with agriculturally acceptable ingredients, wherein the composition of esters are formed from mono, di, tri, tert- or higher order based on the number of available hydroxyl groups in the sugar, sugar alcohol moieties; wherein the nonanoate esters of sugar or sugar alcohol is present in a concentration ranging from 0.1% to 4% by weight of the composition; agriculturally acceptable ingredients are present in a concentration ranging from 0.1% to 96% by weight of the composition; and water in a concentration ranging from 0 to 90%.

2. The bio-pesticidal composition as claimed in claim 1, wherein the Nonanoate esters of sugars and sugar alcohols are selected from the group consisting of Erythritol Nonanoates, Xylitol Nonanoates, Sorbitol Nonanoates, Mannitol Nonanoates, Sucrose Nonanoates, Fructose Nonanoates, Glucose Nonanoates, Psicose Nonanoates, Xylose Nonanoates, Lactose Nonanoates, Galactose Nonanoates and Mannose Nonanoates.

3. The bio-pesticidal composition as claimed in claim 1, wherein the Nonanoate esters of sugar or sugar alcohol is Erythritol esters.

4. The bio-pesticidal composition as claimed in claim 1, wherein the Nonanoates esters of Erythritol is selected from the group consisting of Mono ester of erythritol nonanoate, Di ester of erythritol nonanoate, Tri ester of erythritol nonanoate and Tetra ester of erythritol nonanoate or combinations thereof.

5. The bio-pesticidal composition as claimed in claim 1, wherein the compositions optionally combined with seed treatment nutrient solutions to offer better germination and protection of the saplings against various pests at their early stages of growth.

6. The bio-pesticidal composition as claimed in claim 1, wherein the agriculturally acceptable ingredients are selected from the group consisting of i) Oxidation pathway inhibitors such as gallic acid or tannic acid for reducing resistance, ii) Other insecticides/pesticides natural or synthetic, plant nutrients, stimulants, hormones, PGR etc., iii) Pheromones, iv) Surfactants, spreaders, stickers, penetrants etc., v) Carrier oil, vi) anti-oxidants such as ethoxyquin, a tocopherol, BHT etc., vii) Arginine, Lysine, Glycine, nitrosglutathione, sodium nitrospruside, sodium hydrogen sulphide which may act as adjuvents, viii) Nonionic, Cationic and Anionic surfacts such as Tween (Poly sorbate), or any secondary alcohol ethoxylate, Tergitol (anionic sulfonate), spreading agents such as Silwet (Polyalkyleneoxide modified heptamethyltrisiloxane) and long chain alcohol ranging from C 8 to C 20.

7. The bio-pesticidal composition as claimed in claim 1, wherein the composition comprising nonanoate esters of sugar/sugar alcohols formulated as an insecticidal soap along with agriculturally acceptable excipients selected from the group consisting of surfactants, carrier oil, anti-oxidants such as ethoxyquin, a tocopherol, BHT etc.

8. The bio-pesticidal composition as claimed in claim 1, wherein the compositions can be formulated into liquids, soaps, pellets, granules, suspensions, gels, solutions and aerosol sprays.

9. A process for the preparation of nonanoate esters of sugar and sugar alcohols are prepared by a process comprising the steps of, a) reacting sugar/sugar alcohol with nonanoic acid or its acid chloride in a ratio of 1:0.9 to 1:7 in presence of a suitable solvent and reagents selected from the group consisting of acid catalyst, base catalyst, metal salt, Mitsunobu coupling, carbodimide coupling, carbonyl diimidazole (CDI), Lipase, Lews acid; and b) recovering the nonanoate esters of sugars or sugar alcohol.

10. The process as claimed in claim 9, wherein the suitable solvents may be selected from the group consisting of polar aprotic solvents selected from DMF, DMSO and acetonitrile

11. The process as claimed in claim 9, wherein the Nonanoates esters of sugar and sugar alcohols are prepared by a process comprising the steps of; (i) Adding Sugar/sugar alcohol to nonanoic acid in a ratio of 1:0.9 to 1:7 and heating the resultant mixture at a temperature ranging from 130 C. to 180 C., (ii) Adding 10 to 30% moles of Phosphoric acid with respect to sugar/sugar alcohol into the mixture of step (i), followed by heating for 8 to 48 h, (iii) Cooling the mixture of step (ii) to 60-70 C., followed by diluting with ethyl acetate, (iv) Treating the mixture of step (iii) with Ca(OH).sub.2 for 10 min at this temperature and (v) Filtering the hot solution through celite bed followed by concentrating the filtrate under vacuum to obtain nonanoate esters of sugars or sugar alcohol.

12. The process as claimed in claim 9, wherein the Nonanoate esters of sugar and sugar alcohols are prepared by a process comprising of reaction of sugar/sugar alcohol and nonanoic acid in presence of carbonyl diimidazole (CDI) in DMF at 0-5 C.

Description

DESCRIPTION OF DRAWINGS

[0024] FIG. 1 shows IR spectroscopic data of Erythritol nonanoate

[0025] FIGS. 2 and 3 shows the cumulative overlaid IR data of all sugar nonanoates

[0026] FIG. 4 shows GC chromatogram of Erythritol nonanoates prepared by example 1

[0027] FIG. 5 depicts GC chromatogram of Erythritol nonanoates prepared by example 4

[0028] FIG. 6 depicts GC chromatogram of xylitol and sorbitol nanonoates

[0029] FIG. 7 depicts GC chromatogram of mannitol and sucrose nanonoates

[0030] FIG. 8 depicts GC chromatogram of fructose and glucose nanonoates

[0031] FIG. 9 depicts GC chromatogram of psicose and xylose nanonoates

[0032] FIG. 10 depicts GC chromatogram of lactose and galactose nonanoates

[0033] FIG. 11 depicts GC chromatogram of mannose nanonoates

[0034] FIG. 12 shows 1HNMR of Monoester of Erythritol nonanoate

[0035] FIG. 13 shows 1HNMR of Diester of Erythritol nonanoate

[0036] FIG. 14 shows 1HNMR of Tetra ester of Erythritol nonanoate

[0037] FIG. 15 showing partial acylation of sugar and sugar alcohols

[0038] FIG. 16 shows the result of a field experiment conducted with EN2 formulation on cotton sucking insects' viz. Thrips (Scirtothrips dorsails), Jassids (Amrascabi guttula) and whitefly (Bemisia tabaci).

DETAILED DESCRIPTION OF THE INVENTION

[0039] The invention now will be described in detail in connection with certain preferred and optional embodiments, so that various aspects thereof may be more fully understood and appreciated.

[0040] The present invention discloses novel nonanoate esters of sugar or sugar alcohol useful in pest management, their preparations, compositions containing the same and application in controlling pests and weeds.

[0041] In an embodiment, the sugars and sugar alcohols are selected from the group comprising of sucrose, lactose, glucose, galactose, maltose, fructose, cellobiose, globabiose, psicose, sorbitol, mannitol, xylitol, erythritol etc. either in their chiral pure form or racemic form and any polyhydroxy compounds which are of synthetic or natural in origin.

[0042] In an embodiment, the nonanoates esters of sugar or sugar alcohol may be selected from the group consisting of Erythritol Nonanoates, Xylitol Nonanoates, Sorbitol Nonanoates, Mannitol Nonanoates, Sucrose Nonanoates, Fructose Nonanoates, Glucose Nonanoates, Psicose Nonanoates, Xylose Nonanoates, Lactose Nonanoates, Galactose Nonanoates and Mannose Nonanoates.

[0043] In one of the preferred embodiments, the sugar or sugar alcohol is Erythritol.

[0044] In an embodiment, the invention encompasses hither to unreported novel nonanoate esters of Erythritol. The novel nonanoate esters of Erythritol includes mono, di, tri and tetra esters. These esters are further isolated and subjected to characterization.

[0045] Accordingly, the invention provides mono ester of erythritol nonanoate of the following formula.

##STR00001##

[0046] In another embodiment, the invention provides diester of erythritol nonanoate of the following formula.

##STR00002##

[0047] In yet another embodiment, the invention provides tetraester of erythritol nonanoate of the following formula.

##STR00003##

[0048] In another embodiment, the invention provides a process for the preparation of nonanoate esters of sugars and sugar alcohols which comprises the steps of,

a) reacting sugar/sugar alcohol with nonanoic acid or its acid chloride in a ratio of 1:0.9 to 1:7 in presence of a suitable solvent and a catalyst selected from the group consisting of acid catalyst, base catalyst, metal salt, Mitsunobu coupling, carbodiimide coupling, carbonyl diimidazole (CDI) coupling, Lipase and Lewis; and
b) Isolating the nonanoate esters of sugar or sugar alcohol.

[0049] Accordingly, the said esters can be prepared using acid catalyzed trans-esterification employing the use of an acid catalyst such as phosphoric acid, sulfuric acid, p-toluene sulphonic acid, pyridinium sulphonate, or base catalyzed reactions employing the use of metal carbonate selected from the group consisting of sodium carbonate, potassium carbonate or metal alkoxides selected from the group consisting of sodium or potassium methoxide, ethoxide, potassium tert-butoxide or using metal salts such as zinc chloride, iron chloride, or by Mitsunobu coupling, carbodiimide coupling, carbonyl diimidazole (CDI) coupling, Lipase, and Lewis acids selected from the group of salts of zinc, copper, tin, iron, scandium and gallium.

[0050] The suitable solvents for the reaction may be selected from the group consisting of polar aprotic solvents such as DMF, DMSO, acetonitrile etc.

[0051] In a preferred embodiment, the present invention discloses a process for preparing nonanoate esters of sugars and sugar alcohols comprising; [0052] (i) Adding sugar/sugar alcohol to nonanoic acid in a variable ratio of 1:0.9 to 1:7 and heating the resultant mixture at a temperature ranging from 110 C. to 180 C., [0053] (ii) Adding 10-30% moles of Phosphoric acid (with respect to sugar/sugar alcohol) into the mixture of step (i), followed by heating for 8 to 48 h, [0054] (iii) Cooling the mixture of step (ii) to 60-70 C., followed by diluting with ethyl acetate, [0055] (iv) Treating the mixture of step (iii) with Ca(OH).sub.2 for 10-30 min at this temperature and [0056] (v) Filtering the hot solution through celite bed followed by concentrating the filtrate under vacuum to obtain nonanoate esters of sugars or sugar alcohol.

[0057] The nonanoate esters of sugars or sugar alcohol thus obtained after drying under vacuum was further evaluated for its insecticidal properties.

[0058] In a specific embodiment, the addition of 1.0 equivalents of sugar/sugar alcohols to 0.9 equivalent of nonanoic acid is sufficient to achieve differently substituted nonanoate esters of sugar or sugar alcohol in very good yield.

[0059] In an embodiment, the sugars and sugar alcohols are selected from the group comprising of sucrose, lactose, glucose, galactose, maltose, fructose, cellobiose, globabiose, psicose, sorbitol, mannitol, xylitol, erythritol etc. (Without limitations to the listed sugar and sugar alcohols) either in their chiral form or racemic form and any polyhydroxy compounds which are of synthetic or natural in origin.

[0060] In another embodiment, the nonanoic acid can be used either alone or in combinations with other fatty acids. The degree of acylation having mono, di, tri, tertra or higher order based on the number of available hydroxyl groups in the sugar, sugar alcohol moieties with respect to the ratio of acids available.

[0061] In an alternative embodiment, nonanoate esters of sugar/sugar alcohol were made using acid chloride method where in 1.0 equivalent of nonanoic acid chloride was added to a hot and stirred solution of sugar/sugar alcohol (1.1 equivalent) in dry DMF and pyridine. The mixture was stirred at 80 C. until all the acid chloride was consumed. It was cooled to rt and diluted with ethyl acetate (5 v), washed with water, followed by dilute HCl, then with cold bicarbonate solution and finally with brine. Organic phase separated, dried (anhydrous sodium sulphate), filtered and evaporated under vacuum. The residue thus obtained was used as such for further studies.

[0062] In another embodiment, the said esters can also be prepared using carbonyl diimidazole (CDI) in DMF at 0-5 C. To a solution of nonanoic acid (0.9 equivalent) in DMF was added N,N carbodiimidazole (CDI, 1.2 equivalent) in aliquotes under nitrogen atmosphere. The temperature of the reaction mixture was maintained at 0-5 C. during the addition of CDI. After the complete addition of CDI, the reaction mixture was stirred for 10 min at 0-5 C. under nitrogen atmosphere. Into this was added Erythritol (1.0 equivalent) in aliquots. It was stirred for 24 h, treated with ice cold water and extracted with ethyl acetate. Organic phase separated, washed with saturated brine solution and dried over anhydrous sodium sulfate. Volatiles were removed under reduced pressure to give mixtures of esters as light brown material.

[0063] In another embodiment, the composition comprises nonanoate ester with silica, nano silica diatomaceous earth for the control of pest and insects.

[0064] In another embodiment, the present invention provides a composition comprising sugar/sugar alcohol esters with seed treatment nutrient agents to offer better germination and protection of the seedlings against various pests at their early stages of growth (0-14 days) which are present in the soil.

[0065] In another preferred embodiment, the present invention provides a composition comprising sugar/sugar alcohol esters, specifically a composition comprising nonanoates of sugar/sugar alcohol esters along with other agriculturally acceptable ingredients selected from the following: [0066] a) Oxidation pathway inhibitors such as gallic acid or tannic acid for reducing resistance, [0067] b) Other insecticides/pesticides natural or synthetic, [0068] c) Plant nutrients, stimulants, hormones, PGR etc., [0069] d) Pheromones, [0070] e) Surfactants, spreaders, stickers, penetrants etc., [0071] f) Carrier oil, [0072] g) Anti-oxidants such as ethoxyquin, a tocopherol, BHT, etc., [0073] h) Arginine, Lysine, Glycine, nitrosglutathione, sodium nitrospruside, sodium hydrogen sulphide which may act as adjuvents, [0074] i) Nonionic, Cationic and Anionic surfacts such as Tween (Poly sorbate), or any secondary alcohol ethoxylate, Tergitol (anionic sulfonate), spreading agents such as Silwet (Polyalkyleneoxide modified heptamethyltrisiloxane) and long chain alcohol ranging from C 8 to C 20.

[0075] Accordingly, the present invention provides a final composition comprising sugar/sugar alcohol esters in a concentration ranging from 0.1 to 4% by weight of the composition. The other elements including excipients in the present composition ranging from 0.1% to 96% by weight of the composition and water in a concentration ranging from 0 to 90%.

[0076] Accordingly, the present composition can be formulated as liquids, soaps, pellets, granules, suspensions, gels, solutions and aerosol sprays.

[0077] In another preferred embodiment, the present invention provides composition comprising nonanoate esters of sugar/sugar alcohols formulated as an insecticidal soap along with agriculturally acceptable excipients selected from the group consisting of surfactants, carrier oil, anti-oxidants such as ethoxyquin, a tocopherol, BHT, etc.

[0078] The present invention is explained further in detail by illustrating examples below.

[0079] Some typical examples illustrating the embodiments of the present invention are provided; however, these are exemplary only and should not be regarded as limiting the scope of the present invention.

Example 1: General Procedure for the Preparation of Sugar Nonanoates Using Acid Catalysis

Preparation of Erythritol Nonanoate

[0080] Nonanoic acid (4.7 kg, 29.77 moles) was charged into a three necked RB (10 L) fitted with a short distillation head and a mechanical stirrer. Into this was added erythritol (4.0 kg, 32.75 moles) in aliquots. The reaction mixture was heated to 120 C. Into this was added phosphoric acid drop wise (10 mole percent, with respect to Erythritol) under stirring. The temperature of the reaction mixture slowly raised to 150 C. and stirred for 30 h. It was allowed to reach rt, diluted with ethyl acetate (6.0 L) and treated with calcium hydroxide (242 g). It was filtered through celite bed and the filtrate dried (anhydrous sodium sulphate), evaporated under reduced pressure and dried to give an amber colored viscous liquid. Yield: 7.2 kg.

GC Analysis of Erythritol Nonanoates:

[0081]

TABLE-US-00001 Percentage SL. Compositions in the No. and RT mixture 1 Erythritol nonanoate 10.30% monoestser @ 17.6 3 Erythritol nonanoante 29.82% diestser @ 22.70 (Positional isomer) 4 Erythritol nonanoante 42.70% tetra estser @ 12.45 Positional isomer)

Example 2: General Procedure for the Preparation of Sugar Nonanoates Using Acid Chloride Method

Preparation of Xylitol Nonanoate

[0082] A solution of nonanoyl chloride (19.4 g, 0.11 mole) in acetonitrile (115 mL) was added to a suspension of xylitol (20.0 g, 0.12 mol) in DMF (100 mL) and pyridine (32.0 mL) at rt. It was stirred for 24 h during which TLC showed the disappearance of the starting materials. It was treated with cold water (400 mL) and extracted with ethyl acetate (2100 mL). The organic phases combined, combined phase washed with cold dil. HCl (10 mL3) followed by brine (50 mL2) and then dried (anhydrous sodium sulphate). It was filtered and the filtrate evaporated to dryness to give an off white viscous liquid. Yield: 30.0 g. The individual esters of Xylitol nonanoates thus obtained are not separated and used as such for the preparation of insecticidal formulation; GC analysis shows the formation of mixed esters as expected.

GC Analysis Data of Xylitol Nonanoates:

[0083]

TABLE-US-00002 SL. Retension No. time (min) Composition 1 11.85 54.0% 2 16.87 05.5% 3 17.09 17.7% 4 21.07 07.8% 5 21.64 12.3%

Example 3: General Procedure for the Preparation of Sugar Nonanoates Using N,NCarbodiimidazole

Preparation of Fructose Nonanoates

[0084] To a stirred solution of nonanoic acid (20.0 g, 126 mmole) in DMF (120 mL) was added N,N carbodiimidazole (CDI) (24.5 g, 150 mmole) in aliquots at 0-5 C. After 10 min, was added fructose (7.6 g, 42 mmole) in small portions. The reaction mixture allowed to reach rt and the mixture stirred for further 24 h, during which TLC showed the disappearance of the starting materials. Reaction was quenched by the addition of ice cold water and the content was extracted with ethyl acetate (100 mL3). The organic phases combined and combined phase washed with saturated brine and dried (anhydrous sodium sulfate). Volatiles were removed under reduced pressure to yield a light brown syrupy material. The individual esters of sugar nonanoates thus obtained are not isolated and used as such for the insecticidal formulation. GC analysis indicates the formation of mixed esters, as shown below. Yield 22 g.

GC Analysis of Data Fructose Nonanoates:

[0085]

TABLE-US-00003 SL. Retension No. time (min) Composition 1 5.39 8.3% 2 8.97 9.7% 3 11.87 81.9%

GC Analysis of Data Erythritol Nonanoates:

[0086]

TABLE-US-00004 SL. Name of the No. compound and RT Composition 1 Erythritol nonanoate 41.8% monoestser @ 17.79 3 Erythritol nonanoante 08.8% diestser @ 23.02 (Positional isomer) 4 Erythritol nonanoante 04.9% diestser @ 23.19 (Positional isomer) 5 Erythritol nonanoate 04.5% tetra ester @ 12.3

GC Analysis of Data Sucrose Nonanoates:

[0087]

TABLE-US-00005 SL. Retension No. time (min) Composition 1 05.4 08.3% 2 11.18 09.7% 3 11.81 81.9% 4 22.54 09.6% 5 24.77 05.3%

[0088] The following nonanoate esters of sugars were prepared using one of the above mentioned methods:

[0089] Erythritol Nonanoates, Xylitol Nonanoates, Sorbitol Nonanoates, Mannitol Nonanoates, Sucrose Nonanoates, Fructose Nonanoates, Glucose Nonanoates, Psicose Nonanoates, Xylose Nonanoates, Lactose Nonanoates, Galactose Nonanoates, Mannose Nonanoates.

Analytical Data:

[0090] The density of sugar esters varies between 0.96 to 01.04 g/mL.

TABLE-US-00006 TABLE 1 Sl. No. Compound Name Density 1 Erythritol Nonanoates 1.01 g/mL @ 30 C. 2 Xylitol Nonanoates 0.98 g/mL @ 30 C. 3 Sorbitol Nonanoates 0.99 g/mL @ 30 C. 4 Mannitol Nonanoates 0.99 g/mL @ 30 C. 5 Sucrose Nonanoates 1.04 g/mL @ 30 C. 6 Fructose Nonanoates 0.99 g/mL @ 30 C. 7 Glucose Nonanoates 0.98 g/mL @ 30 C. 8 Psicose Nonanoates 0.96 g/mL @ 30 C. 9 Xylose Nonanoates 0.98 g/mL @ 30 C. 10 Lactose Nonanoates 0.99 g/mL @ 30 C. 11 Galactose Nonanoates 0.99 g/mL @ 30 C. 12 Mannose Nonanoates 1.01 g/mL @ 30 C.

[0091] The FTIR further confirmed the formation of esters.

GC Analysis Data

[0092] GC analysis was done for all the crude samples of sugar nonanoates. The column used is ZB5 30m0.25 mm0.25 m, Make Phenomenex. Injector temperature 250 C., Detector temperature 300 C., Column Flow 1 mL/min, Carrier gas Nitrogen, Injection volume is 1 L.

[0093] From G.C analysis data it is evident that polyhydroxy sugar and sugar alcohols undergone esterification with nonanoic acid either partially or fully leading to the formation of mixtures of mono, di, tri and tetra esters in varying proportions. The mixture of esters may be also formed from different regio isomers.

[0094] This composite mixture of nonanoate esters in different proportions is very powerful insecticidal agents, whose activity is clearly explained in entomological studies. Moreover, since the composite mixtures are used as such, without subjecting to isolation of individual esters; the composition of these insecticidal agents are cost effective.

Chromatographic Purification

[0095] The crude erythritol nonanoates prepared by example 1 and 4 were subjected to silica gel column chromatography (100-200 mesh, Make SD Fine Chemicals) purification using Ethyl Acetate-Hexane (30 to 70%) as eluent. The fractions were collected, evaporated, dried and characterized using H NMR.

[0096] The .sup.1HNMR data of these esters are given below.

[0097] .sup.1HNMR of monoester of Erythritol nonanoate: (500 MHz, CDCl.sub.3) 0.88 (3H, t, J 1=6.9 Hz), 1.3 (10H, m), 1.64 (2H, m), 2.37 (2H, t, J 1=7.6 Hz), 2.72 (1H, s), 3.76 (1H, s), 4.33 (2H, t, J 1=1.9 Hz) (FIG. 12)

[0098] .sup.1HNMR of Diester of Erythritol nonanoate: (500 MHz, CDCl.sub.3) 0.88 (6H, t, J 1=6.8 Hz), 1.28 (22H, m), 1.64 (4H, m), 2.37 (4H, t, J 1=7.6 Hz), 2.69 (2H, d, J 1=4.5 Hz), 3.76 (2H, t, J 1=4.4), 4.33 (4H, t, J 1=3.4 Hz) (FIG. 13)

[0099] .sup.1HNMR of tetraester of Erythritol nonanoate: (500 MHz, CDCl.sub.3) 0.88 (12H, t, J 1=6.9 Hz), 1.28 (42H, m), 1.63 (8H, m), 2.33 (8H, m) (FIG. 14)

[0100] Entomological studies were carried out on different pests using various nonanoate esters of sugar/sugar alcohols@ 0.25%; 0.5% and at 1% concentration and the mortality rate is observed after 48 h, as shown in table 2 to 4. The following pests were selected for entomological studies:

[0101] 1. Fall armyworm (Spodoptera frugiperda)

[0102] 2. Cotton pink bollworm (Pectinophora gossypiella)

[0103] 3. Corn leaf aphid (Rhopalosiphum maidis)

[0104] 4. Hibiscus mealybug (Maconellicoccus hirsutus)

TABLE-US-00007 TABLE NO. 2 Mortality rate @ 0.25% concentration after 48 h Fall Army Cotton pink Compound Name worm bollworm Aphids Mealybug Erythritol Nonanoate Very Good Minimal Very good Minimal Xylitol Nonanoate Excellent Minimal Good Minimal Sorbitol Nonanoate Excellent Very good Good Minimal Mannitol Nonanoate Excellent Minimal Good Minimal Sucrose Nonanoate Excellent Minimal Minimal Minimal Fructose Nonanoate Excellent Minimal Minimal Minimal Glucose Nonanoate Minimal Minimal Minimal Minimal Psicose Nonanoate Minimal Minimal Minimal Minimal Xylose Nonanoate Minimal Minimal Minimal Minimal Lactose Nonanoate Minimal Minimal Minimal Minimal Galactose Nonanoate Minimal Minimal Minimal Minimal Mannose Nonanoate Very Good Minimal Minimal Minimal Delegate (1 ml/L, Excellent Excellent Excellent Excellent Market control)

TABLE-US-00008 TABLE NO. 3 Mortality rate @ 0.5% concentration after 48 h Fall Army Cotton pink Compound Name worm bollworm Aphids Mealybug Erythritol Nonanoate Very Good Minimal Excellent Minimal Xylitol Nonanoate Excellent Minimal Very Good Minimal Sorbitol Nonanoate Excellent Excellent Very Good Minimal Mannitol Nonanoate Excellent Very Good Very Good Minimal Sucrose Nonanoate Excellent Very Good Minimal Minimal Fructose Nonanoate Excellent Minimal Minimal Minimal Glucose Nonanoate Minimal Minimal Minimal Minimal Psicose Nonanoate Very Good Minimal Very Good Minimal Xylose Nonanoate Minimal Minimal Minimal Minimal Lactose Nonanoate Minimal Very Good Minimal Very Good Galactose Nonanoate Minimal Minimal Minimal Minimal Mannose Nonanoate Very Good Very Good Minimal Minimal Delegate (1 ml/L, Excellent Excellent Excellent Excellent Market Control)

TABLE-US-00009 TABLE NO. 4 Mortality rate @ 1% concentration after 48 h Fall Army Cotton pink Compound Name worm bollworm Aphids Mealybug Erythritol Nonanoate Very Good Minimal Excellent Minimal (EN) Xylitol Nonanoate Excellent Minimal Very Good Minimal Sorbitol Nonanoate Excellent Excellent Excellent Very Good Mannitol Nonanoate Excellent Excellent Excellent Minimal Sucrose Nonanoate Excellent Excellent Minimal Minimal Fructose Nonanoate Excellent Very Good Minimal Very Good Glucose Nonanoate Minimal Minimal Minimal Very Good Psicose Nonanoate Very Good Minimal Very Good Minimal Xylose Nonanoate Minimal Minimal Minimal Minimal Lactose Nonanoate Minimal Excellent Minimal Excellent Galactose Nonanoate Excellent Minimal Very Good Minimal Mannose Nonanoate Excellent Excellent Very Good Minimal Delegate (1 ml/L, Excellent Excellent Excellent Excellent Market control)

[0105] 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.

[0106] While the market control Delegate is 11.7% SC concentration; the claimed formulations are tested with 0.25 to 1% concentration. The active, Spinetoram in the Delegate is a synthetic product, whereas, the claimed compositions are of organic in nature. Also, the claimed compositions are cheapest in the light of cost effective synthesis, easily available raw materials and the lower amount of the active ingredient required to achieve the pesticidal activity and also with no toxic effect to aquatic, mammalian and the plants and hence it is safe to use as well as safe to consume the produce of such treated plants.

[0107] The following Erythritol Nonanoate (EN-formulations) were prepared, wherein, EN refers to the Erythritol nonanoate esters prepared as per example 1

TABLE-US-00010 TABLE NO. 5 Sl. No. Code Formulation Details 1 EN-1 EN + Tergitol + Silwet + Water (8 g + 200 mg + 200 mg + 2 mL) 2 EN-2 EN1 + Arginine (5 mL + 400 mg) 3 EN-3 EN1 + Gallic Acid (5 mL + 400 mg) 4 EN-4 EN1 + Arginine + Gallic Acid (5 mL + 400 mg + 400 mg)

[0108] The above mentioned formulations were tested in laboratory (in vivo study) to determine their insecticidal activity against fall armyworm (Spodoptera frugiperda). Positive control (market control) used is Delegate (Spinetoram 11.7% SC); a broad spectrum insecticide from Dow Agrosciences. Negative control used is sterile water. Surface application method (topical) was used for this study. For each formulation three insect larvae were tested. Each larva was dipped into the solution containing active ingredient to ensure the entire body of larva covered by test solution. The effects of the formulations were observed at 17 h, 24 h and 48 h after the application of the product. The mortality rate was determined by counting the number of live and dead insect larva. No mortality was observed for negative control.

[0109] Similar experiment was performed on cotton pink boll worm (Pectinophora gossypiella). The comparative data on two different insects are provided in table 6.

TABLE-US-00011 TABLE NO. 6 Percentage Mortality Rate of EN Formulation Mortality Rate @ 48 h Fall Army Worm Pink boll worm Sample Concentration Concentration Code 0.2% 1% 0.2% 1% Delegate Excellent Excellent Excellent Excellent (Market Control) EN 1 Excellent Excellent Minimal Excellent EN 2 Excellent Excellent Minimal Minimal EN 3 Very Good Excellent Minimal Minimal EN 4 Very Good Excellent Minimal Minimal

Phytotoxicity Study

[0110] The phytotoxicity study was performed on Tomato/Chili plants (Germination to various stages of crop). The formulations were diluted with water and applied by spraying on leaves. Phytotoxicity was carried out by visual observation of leaves before and again at 72 h after spraying. The results of the same are discussed in table 7.

TABLE-US-00012 TABLE NO. 7 Phytotoxicity results of EN Formulation Observation after 72 h of EN spraying Sample Concentration Code 0.2% 0.5% 1.0% 3.0% EN 1 None None None moderate EN 2 None None None moderate EN 3 None None None moderate EN 4 None None None moderate

Phytotoxicity Categories

[0111] NoneNo signs of phytotoxicity
SlightA few scorching or discoloration of leaves
ModerateSignificant scorching spotting or discoloration of leaves but less than 20% of leaf area
SevereSevere scorching or curling of leaves with necrosis

[0112] From above phytotoxicity data it was reflecting that up to 1% concentration these formulations are very safe to use as broad-spectrum insecticide in the tested Tomato/Chili plants.

[0113] A field experiment was conducted with EN2 formulation on cotton sucking insects viz. thrips (Scirtothrips dorsails), aphids (Aphis gossypii), jassids (Amrascabi guttula) and whitefly (Bemisia tabaci), as shown in FIG. 25. Two benchmark insecticides were used as control viz. Thiamethoxam (a broad spectrum insecticide) and Acetamiprid (effective to cotton sucking pest). Three doses of EN 2 formulation (for 1 kg formulation EN 800 g+Arginine 80 g+Silwet20 g+Tergitol 20 g+Water 150 g) was used for this study viz. 1.25 g/L, 2.5 g/L and 5 g/L.

[0114] Initially the population of the pests (pre count) was assessed before spraying. The field was found to be above economic threshold level. The number of major sucking pests (2 leaves from top, one from middle and 2 leaves from bottom) in 5 tagged plants/treatment was recorded at 24 h before the spray and after 24 h, 3.sup.rd, 6.sup.th and 9.sup.th day after spray. The data was pooled and average population calculated.

Effect of EN2 on Thrips Population

[0115] EN 2 reduced the thrips population by 15.18% as compared to Thiamethoxam (15.9%) and Acetamiprid (13.7%) after 24 h. On 3.sup.rd day of application, EN 2 @ 5 g/L reduced the thrips population by 28.85% as compared to 31.6% by Thiamethoxam. Acetamiprid reduced the thrips population by 19.76%. At 6.sup.th and 9.sup.th days observation also showed that EN 2 gave almost on par effect as that of Thiamethoxam and Acetamiprid. The results are discussed below in Table 8. Thiamethoxam and Acetamiprid are also synthetic compounds similar to Spinetoram when compared to the current biopesticide compositions, which is of organic in nature. Therefore, the biopesticide compositions are safe to use and also safe to consume the produce of such treated plants. Further, the biopesticide composition of the present invention does not leave any residue either on the plant or on the produce and thus safe. Further, the composition of the present invention is cost-effective when compared to the existing marketed products as the the production of the same is industrially scalable by using readily available raw materials, as demonstrated in the invention. Also, the Nonanoate esters formed in the process of the present invention can be used as such and no need for the separation of individual esters thereby further reduces the cost of the manufacturing process and thus the product.

TABLE-US-00013 TABLE NO. 8 Thrips population count after spray Sl. Sample Name & Pre- 3rd 6th 9th No. Dose treatment 24 h day day day 1 EN 2 @ 1.25 g/L 29 22.9 4.53 5.53 3.56 2 EN 2 @ 2.5 g/L 28 26.7 4.43 5.53 3.73 3 EN 2 @ 5 g/L 25 26 3.6 5.66 3.4 4 Thiamethoxam 28 23.7 3.46 5.33 3.76 @ 0.5 g/L 5 Acetamiprid 30 22.7 4.06 5.66 3.6 @ 0.5 g/L 6 Control 29 27 5.06 6.6 6.26

Effect of EN 2 on Jassids Population

[0116] EN 2 reduced the Jassids population by 8.9% on 3.sup.rd day after the spray against 11.8% by Thiamethoxam. However at 9.sup.th day, Thiamethoxan reduced the Jassid population by 40.6% as compared to EN 2 reduced the population by 29.1%. EN 2 spray gave almost similar Jassid population to Acetamiprid application. The results are discussed in Table 9.

TABLE-US-00014 TABLE NO. 9 Jassids population count after spray Sl. Sample Name & Pre- 3rd 6th 9th No. Dose treatment 24 hrs day day day 1 EN 2 @ 1.25 g/L 13.66 11.66 3.6 2.13 3.06 2 EN 2 @ 2.5 g/L 14.66 11.33 3.93 2.33 3.33 3 EN 2 @ 5 g/L 13 .. 33 9 3.4 2.53 3.4 4 Thiamethoxam 16.33 13.66 3.26 2 2.73 @ 0.5 g/L 5 Acetamiprid 16.33 14 3.56 2.66 3.36 @ 0.5 g/L 6 Control 14.33 14 4.83 2.53 4.6

Effect of EN 2 on Whitefly Population

[0117] EN 2 from Insects spray significantly reduced the Whitefly population, which was almost on par to Thiamethoxan and Acetamiprid, as shown in table 10.

TABLE-US-00015 TABLE NO. 10 Whitefly population count after spray Sl. Sample Name & Pre- 3rd 6th 9th No. Dose treatment 24 h day day day 1 EN 2 @ 1.25 g/L 11.66 11 2.06 2.6 1.86 2 EN 2 @ 2.5 g/L 11.33 9.66 1.9 2.93 1.4 3 EN 2 @ 5 g/L 9 8.66 1.6 2.13 1.66 4 Thiamethoxam 13.66 7 1.86 2.46 1.7 @ 0.5 g/L 5 Acetamiprid 14 8.66 1.66 2.4 2.13 @ 0.5 g/L 6 Control 14 12 3.7 3.26 3.66

Method of Seed Treatment:

[0118] A mixture of nutrient solution (2.5 mL) and erythritol nonanoate esters (1 mL) were mixed well, applied on maize seeds (1.0 kg), tested for germination and protection in soil for 15 days. The same procedure repeated by increasing the quantity of erythritol nonanoate esters per kg of the seeds and tested again.

[0119] Table 11 shows the results of seeds treated with a combination of nutrient and erythritol nonanoates against Fall Army Worm.

TABLE-US-00016 TABLE 11 Evaluation of Trail Blaze and Ecolaid freedom on Maize seedKharif 2021 on Fall Army Worm control S. Dosage/kg 12.sup.th 13.sup.th 14.sup.th No. Treatment of seed day day day 1 Trail Blaze 2.5 mL 4 4 19 (TB) 2 TB + EN 2.5 mL + 4 4 16 1.0 mL 3 TB + EN 2.5 mL + 4 7 16 2.0 mL 4 TB + EN 2.5 mL + 4 5 16 5.0 mL 5 TB + Neem 2.5 mL + 5 5 20 powder 50 g 6 Control 7 7 22

[0120] The data reflects that Trial Blaze (TB) (seed coating nutrient solution) in combination of EN controlling fall army worm on maize seedlings up to 14th days when the seedlings are more vulnerable to pest attack. It shows the seedlings become more resistant to pest attack.