Bio-insecticides from waste biomass

Abstract

Disclosed herein are bio-based insecticide compositions for more sustainable pest management practices that contain carbamate compounds. Processes for producing these bio-based insecticide compositions are also disclosed.

Description

[0001] BIO-INSECTICIDES FROM WASTE BIOMASS

[0002] CROSS-REFERENCE TO RELATED APPLICATION

[0003] This application claims priority to United States Provisional Application No. 63 / 513,143, filed July 12, 2023, and the contents of which are incorporated herein by reference in their entireties for all purposes.

[0004] FIELD

[0005] The present disclosure relates to bio-based insecticide compositions for more sustainable pest management practices and methods for producing these bio-based insecticide compositions.

[0006] BACKGROUND

[0007] To meet rising population trends, worldwide crop production is projected to increase by 70% by 2050. The current Global Insecticide Market is 18.47 billion USD and, as a consequence of rising population trends, the demand for agricultural insecticides will increase. The carbamate insecticides market size is forecasted to reach a value of $341 .6 million by the end of 2027, growing at a compound annual growth rate of 4.5%. This market trend poses a significant environmental threat as commercial carbamate insecticides are synthesized from petroleum derived aromatics and produced from fossil fuel-derived phenols, such as cresol (V. Gagicet al., Proc. Natl. Acad. Sci. U.S.A., 2021 , 118). Commonly used insecticides such as fenitrothion, Amitraz and chlorpropham are derived from fossil fuels and are commercially priced at $70 to $240 per gallon. Synthesis of these insecticides involve the use of strong acids (e.g., nitric and sulfuric acids) that ultimately play into the production of toxic waste streams resulting in ecological damage (A. S. Nile et al., Environ. Sci. Pollut. Res., 2019, 26, 21127-21 139).

[0008] Bio-based insecticides are a more sustainable and often safer alternative for pest management in agricultural production. Unfortunately, progress in this field is rather limited. Bio-oils obtained from the pyrolysis of biomass and other mild fungicides derived from reductive catalytic fractionation of lignin have only been explored. Additionally, the insecticidal activity of these compounds is several orders of magnitude lower than that of commercial insecticides. Thus, to address the foregoing issues, we disclose herein bio-based insecticide compositions for more sustainable pest management practices and methods for producing these bio-based insecticide compositions.

[0009] SUMMARY

[0010] Disclosed herein is a process for preparing a bio-based carbamate insecticide that includes (i.e. , comprises) at least one or more of performing a reductive amination reaction on an aldehyde to produce an amine product; and subjecting the amine product to a carbonylation reaction to produce the bio-based carbamate insecticide.

[0011] Disclosed herein are also compositions including at least one bio-based carbamate insecticide prepared by the methods disclosed herein.

[0012] BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Other features and advantages of the compositions, devices and methods disclosed herein will be apparent to those skilled in the art reading the following detailed description in conjugation with the exemplary embodiments illustrated in the drawings, wherein:

[0014] FIG. 1 depicts a reaction network for an exemplary reductive amination reaction with vanillin.

[0015] FIG. 2 depicts a catalyst screening and optimizations for an exemplary reductive amination reaction with vanillin. (A) Catalyst Screening Conditions: 7.5 mL liquid ammonia, 0.4 g vanillin, 0.05 g catalyst, 100°C, 60 minutes, 40 bar H2, 800 rpm. (B) reaction conditions: 7.5 mL liquid ammonia, 0.4 g vanillin, 0.05 g catalyst, 60 minutes, 40 bar H2, 800rpm. (C) reaction conditions: 7.5 mL liquid ammonia, 0.4 g vanillin, 0.05 g catalyst, 60 minutes, 80°C, 800 rpm. (D) reaction conditions: 7.5 mL liquid ammonia, 0.4 g vanillin, 0.05 g catalyst, 80°C, 40 bar H2, 800 rpm.

[0016] FIG. 3 depicts an optimization of an exemplary reductive amination reaction of furfural to furfurylamine.

[0017] FIG. 4 depicts an optimization of an exemplary reductive amination from furfural to furfurylamine. (A) reaction conditions: 7.5 mL liquid ammonia, 0.25 g furfural, 0.05 g Rh / ALOs, 800 rpm stirring, 60 minutes, 80°C. (B) reaction conditions: 7.5 mL liquid ammonia, 0.25 g furfural, 0.05 g Rh / AhOs, 800 rpm stirring, 60 minutes, 40 bar H2. (C) reaction conditions: 7.5 mL liquid ammonia, 0.25 g furfural, 0.05 g Rh / AhOs, 800 rpm stirring, 40 bar H2, 100 °C.

[0018] FIG. 5 depicts recycle runs for an exemplary reductive amination reaction of furfural to furfurylamine. Reaction conditions: 100 °C, 7.5 mL liquid ammonia, 0.25 g furfural, 0.05 g Rh / AhOs, 800 rpm stirring, 60 minutes, 40 bar H2.

[0019] FIG. 6 depicts a reaction mechanism for an exemplary carbonylation reaction of furfurylamine. The reaction mechanism focuses on the coordination of a triflate catalyst to a carbonyl group.

[0020] FIG. 7 depicts a reaction mechanism for an exemplary carbonylation reaction of furfurylamine. The reaction mechanism provides possible byproducts of the exemplary carbonylation reaction.

[0021] FIG. 8 depicts a catalyst screening for an exemplary carbonylation reaction of furfurylamine. Reaction conditions: 80°C, 10 hours, 30 mmol DMC, 3 mmol furfurylamine, 0.15 mmol catalyst, and 800 rpm stirring. Methyl (2- furylmethyl)carbamate (FC), Tris(furan-2-ylmethyl)amine (TA), N-methyl furfurylamine (MFA), and 1-(2-furyl)-N-(2-furylmethyl)methanimine (DA).

[0022] FIG. 9 depicts an optimization of the reactant: solvent molar ratio for an exemplary carbonylation reaction of furfurylamine. Reaction conditions: 80°C, 10 hours, 3 mmol furfurylamine, 0.3 mmol La(OTf)3 and 800 rpm stirring.

[0023] FIG. 10 depicts an optimization of catalyst loading for an exemplary carbonylation reaction of furfurylamine. Reaction conditions: 80°C, 10 hours, 30 mmol DMC, 3 mmol furfurylamine and 800 rpm stirring.

[0024] FIG. 11 depicts an optimization of reaction time for an exemplary carbonylation reaction of furfurylamine. Reaction conditions: 80°C, 30 mmol DMC, 3 mmol furfurylamine, 0.18 mmol La(OTf)s and 800 rpm stirring.

[0025] FIG. 12 depicts a catalyst screening for an exemplary vanillylamine carbonylation reaction. Reaction conditions: 80 °C, 10 hours, 30 mmol DMC, 3 mmol vanillylamine, 0.3 mmol La(OTf)s and 800 rpm stirring.

[0026] FIG. 13 depicts the mortality of adult Alphitobius diaperinus exposed in vial bioassays to carbofuran, methyl (2-furylmethyl)carbamate, or methyl(4-hydroxy-3- methoxybenzyl) carbamate. Lines depict the median lethal concentrations (LCso), and shading depicts the 95% Cl, estimated with probit analysis. FIG. 14 depicts ecotoxicity simulations for commercial carbamate class insecticides compared with exemplary carbamate compounds prepared by the methods disclosed herein. The LCso data was generated for plankton. Methyl (2- furylmethyl)carbamate (FC), methyl(4-hydroxy-3-methoxybenzyl) carbamate(VC).

[0027] FIG. 15 depicts ecotoxicity simulations for commercial carbamate class insecticides compared with exemplary carbamate compounds prepared by the methods disclosed herein. The LCso data was generated for fish. Methyl (2- furylmethyl)carbamate (FC), methyl(4-hydroxy-3-methoxybenzyl) carbamate(VC).

[0028] FIG. 16 depicts ecotoxicity simulations for commercial carbamate class insecticides compared with exemplary carbamate compounds prepared by the methods disclosed herein. The LDso data was generated for rats. Methyl (2- furylmethyl)carbamate (FC), methyl(4-hydroxy-3-methoxybenzyl) carbamate(VC).

[0029] FIG. 17 depicts toxicity simulations for known biopesticide active ingredients compared with exemplary carbamate compounds prepared by the methods disclosed herein. LCso data is for fish. Methyl (2-furylmethyl)carbamate (FC), methyl(4-hydroxy-3-methoxybenzyl) carbamate (VC).

[0030] FIG. 18 depicts toxicity simulations for known biopesticide active ingredients compared with exemplary carbamate compounds prepared by the methods disclosed herein. LDso data is for rats. Methyl (2-furylmethyl)carbamate (FC), methyl(4-hydroxy-3-methoxybenzyl) carbamate (VC).

[0031] FIG. 19 depicts toxicity simulations for known biopesticide active ingredients compared with exemplary carbamate compounds prepared by the methods disclosed herein. LCso data is for plankton. Methyl (2-furylmethyl)carbamate (FC), methyl(4-hydroxy-3-methoxybenzyl) carbamate (VC).

[0032] FIG. 20 depicts possible environmental fates for end-life products for commercial and biobased insecticides prepared by the methods disclosed herein, (a) Carbofuran, (b) Bio-based insecticides prepared by the methods disclosed herein.

[0033] DETAILED DESCRIPTION

[0034] On aspect of the present disclosure is a process for preparing a bio-based carbamate insecticide that includes one or more of performing a reductive amination reaction on an aldehyde to produce an amine product; and subjecting the amine product to a carbonylation reaction to produce the bio-based carbamate insecticide.

[0035] As used herein, the term "bio-based carbamate" refers to any carbamate that is derived from renewable resources (e.g., cellulosic biomass containing lignosulfonates, kraft and / or alkali lignin). For example, a bio-based carbamate can be a carbamate synthesized from an aldehyde purified from the depolymerization of lignosulfonates. Carbamates derived from fossil fuel sources or fossil fuel derived chemicals (e.g., petroleum, crude oil, naphthalene, benzo hydrofurans, and some phenols) are not bio-based carbamates.

[0036] In exemplary embodiments, the bio-based carbamate insecticide is a compound of Formula (I): Formula (I), wherein:

[0037] Ri is H,

[0038] R2is H,

[0039] R3is H, -CH3or -CH2OH, and

[0040] R4 is O, S or NH.

[0041] In exemplary embodiments, the bio-based carbamate insecticide is a compound of Formula (II): Formula (II), wherein: Ri is H,

[0042] R2is H,

[0043] R3is H, -CH3or -CH2OH, and

[0044] R4 is O, S or NH. In exemplary embodiments, the bio-based carbamate insecticide is a compound of Formula (III) Formula (III), wherein:

[0045] Rs is -OCH3, -OH or H, Re is -OCH3, -OH or H, and

[0046] R7is -OCH3, OH or H.

[0047] In exemplary embodiments, the bio-based carbamate insecticide is a compound with a structure of: In exemplary embodiments, the aldehyde used in the reductive amination reaction is:

[0048] In exemplary embodiments, the performing of the reductive amination reaction includes reacting the aldehyde with ammonia under a H2 pressure ranging from about 10 bar to about 100 bar, about 20 bar to about 80 bar, about 30 bar to about 70 bar, about 30 bar to about 60 bar, about 20 bar to about 70 bar, about 20 bar to about 50 bar or any pressure or pressure range falling within about 10 bar to about 100 bar. Those of ordinary skill will appreciate that the H2 pressure can vary based on the equipment used to perform the reductive amination reaction and the scale of the reductive amination reaction. Accordingly, those of ordinary skill would be readily capable of determining the appropriate H2 pressures needed to achieve production of the amine product resulting from the reductive amination reaction. As used herein, the term "about" refers to a value that is ± 5% of the stated value. In addition, it is understood that reference to a range of a first value to a second value includes the range of the stated values, e.g., a range of about 1 to about 5 also includes the more precise range of 1 to 5. It is also understood that the ranges disclosed herein include any selected subrange within the stated range, e.g., a subrange of about 50 to about 60 is contemplated in a disclosed range of about 1 to about 100.

[0049] In exemplary embodiments, the reductive amination reaction occurs for about 20 minutes to about 300 minutes, about 30 minutes to about 240 minutes, about 30 minutes to about 120 minutes, about 30 minutes to about 60 minutes or any time range falling with about 20 minutes to about 300 minutes.

[0050] In exemplary embodiments, the reductive amination reaction occurs for about 12 hours to about 24 hours, for about 12 hours to about 18 hours or for any amount of time falling within the range of about 12 hours to about 24 hours.

[0051] In exemplary embodiments, the reductive amination reaction is performed at a temperature ranging from about 70°C to about 150°C, from about 80°C to about 120°C, from about 80°C to about 100°C or any temperature range falling within the range of about 70°C to about 150°C.

[0052] In exemplary embodiments, the reductive amination reaction is performed in a presence of a catalyst. The catalyst can be selected from, but is not limited to, Rh / AhOs, Pd / C, Ru / C, Ru / ZrO2, Raney Nickel, Rh / C or Pt / C.

[0053] In exemplary embodiments, the subjecting of the amine product to the carbonylation reaction comprises reacting the amine product in a presence of a metal triflate catalyst. The metal triflate catalyst can be selected from, but is not limited to, ytterbium triflate, lanthanum triflate, scandium triflate or zinc triflate. An advantage of using metal triflate catalysts in the carbonylation reaction is that they can coordinate with carbonyl groups via their Lewis acidity, thereby promoting nucleophilic attack at the carbonyl carbon by the amine product produced from the reductive amination reaction. Accordingly, any metal catalyst that can coordinate with carbonyl groups to improve their electrophilicity can be used in the carbonylation reaction. Those of ordinary skill would be readily capable of determining the appropriate metal catalysts to use in the carbonylation reaction for improving the electrophilicity of the carbonyl carbon.

[0054] In exemplary embodiments, the carbonylation reaction is performed in the presence of dimethyl carbonate. Dimethyl carbonate can be present in a concentration ranging from about 20 mmol to about 100 mmol, about 20 mmol to about 60 mmol, about 60 mmol to about 100 mmol or any concentration falling within the range of about 20 mmol to 100 mmol. In exemplary embodiments, dimethyl carbonate is used as the solvent in the carbonylation reaction.

[0055] In exemplary embodiments, the carbonylation reaction is performed in the presence of methyl ch Io reform ate. Methyl chloroformate can be present in a concentration ranging from about 20 mmol to about 100 mmol, about 20 mmol to about 60 mmol, about 60 mmol to about 100 mmol or any concentration falling within the range of about 20 mmol to 100 mmol. In exemplary embodiments, methyl chloroformate is used as the solvent in the carbonylation reaction.

[0056] In exemplary embodiments, the carbonylation reaction occurs for about 4 hours to about 24 hours, for about 8 hours to about 24 hours, for about 8 hours to about 16 hours or for any amount of time falling within the range of about 4 hours to about 24 hours.

[0057] In exemplary embodiments, the carbonylation reaction comprises reacting the amine product with a catalyst (e.g., a metal triflate catalyst) in an amine product: catalyst ratio of about 16:1 , about 15:1 , about 14:1 , about 13:1 , about 12:1 , about 11 :1 , or about 10:1.

[0058] In exemplary embodiments, the carbonylation reaction comprises reacting the amine product with dimethyl carbonate or methyl chloroformate in a dimethyl carbonate or methyl chloroformate: amine product ratio of about 5:1 , about 6:1 , about 7:1 , about 8:1 , about 9:1 , about 10:1 , about 11 :1 , about 12:1 , about 13:1 , about 14:1 , about 15:1 , or about 20:1.

[0059] In exemplary embodiments, the carbonylation reaction comprises reacting the amine product with dimethyl carbonate (DMC) or methyl chloroformate (MC) and a catalyst in a DMC or MC: amine: catalyst ratio of 10:1 :0.1 , 9:1 :0.1 , 8: 1 :0.1 , 7:1 :0.1 , 6:1 :0.1 , 5:1 :0.1 , 10:1 :0.5, 9:1 :0.5, 8:1 :0.5, 7:1 :0.5, 6:1 :0.5, 5:1 :0.5 or 5- 10:1 :0.1-0.5. In exemplary embodiments, the reductive amination reaction produces the amine product in a yield ranging from about 85% to about 100%, about 90% to about 99.9%, about 95% to about 99.9% or about 98% to about 99.9%.

[0060] In exemplary embodiments, the carbonylation reaction produces the biobased carbamate insecticide in a yield ranging from 60% to about 95%, about 70% to about 95%, about 80% to about 95%, about 85% to about 95%, about 90% to about 95%. In exemplary embodiments, the carbonylation reaction produces the bio-based carbamate insecticide in a yield greater than 95%.

[0061] In exemplary embodiments, the process includes isolating the aldehyde from a renewable resource containing lignosulfonates, hemicellulose, kraft and / or alkali lignin. Processes for isolating aldehydes and other compounds from renewable resources containing lignosulfonates, kraft and / or alkali lignin can be found in D. Bourbiaux et al. (D. Bourbiaux, J. Pu, F. Rataboul, L. Djakovitch, C. Geantet, D. Laurenti, Catal. Today 2021 , 373, 24-37), Fache et al. (M. Fache, B. Boutevin, S. Caillol, ACS Sustain. Chem. Eng. 2015, 4, 35-36), Pacek et al. (A. W. Pacek, P. Ding, M. Garrett, G. Sheldrake, A. W. Nienow, Ind. Eng. Chem. Res. 2013, 52, 8361-8372) and Wang et al. (Y. Wang, S. Sun, F. Li, X. Cao, R. Sun, Ind. Crops Prod. 2018, 116, 116-121 ). In exemplary embodiments, the isolating of the aldehyde from the renewable resource includes one or more of depolymerizing lignosulfonates to produce a reaction mixture containing the aldehyde and precipitating the aldehyde out of the reaction mixture.

[0062] In exemplary embodiments, the renewable resource is a cellulosic biomass. As used herein, the term “cellulosic biomass” refers to virtually any plant-derived organic matter (woody or non-woody) available for energy on a sustainable basis, such as, but not limited to plant biomass. Plant biomass can include, but is not limited to, agricultural crop wastes and residues such as corn stover, aquatic plants (e.g., algae), wheat straw, rice straw, sugar cane bagasse, woody energy crops, wood wastes, residues from trees such as fruit trees and fruit-bearing trees (e.g., apple trees and orange trees), softwood forest thinnings, barky wastes, sawdust, paper and pulp industry waste streams, wood fiber, grass crops, prairie cord grass, switchgrass, miscanthus, big bluestem, little bluestem, side oats grama, yard waste (e.g., grass clippings, leaves, tree clippings, brush, etc.) and vegetable processing waste.

[0063] Another aspect of the present disclosure is an insecticidal composition including at least one bio-based carbamate produced from any one of the processes disclosed herein.

[0064] The insecticidal composition can be used to repel one or more target pest such as, but not limited to, animals belonging to the animal order of Acari, Anoplura, Araneae, Blattodea, Coleoptera, Collembola, Diptera, Grylloptera, Heteroptera, Homoptera, Hymenoptera, Isopoda, Isoptera, Lepidoptera, Mantodea, Mallophaga, Neuroptera, Odonata, Orthoptera, Psocoptera, Siphonaptera, Symphyla, Thysanura, and / or Thysanoptera.

[0065] In exemplary embodiments, the composition has an LCso against adult Alphitobius diaperinus of at least 6,660,622 ng / cm3

[0066] In exemplary embodiments, the insecticidal composition comprises one or more additives selected from, but not limited to, botanical essential oils or concentrates (e.g., camphor oil, litsea cubeba oil, spearmind oil, citronella oil, geranial oil, cassia oil, star anise oil, cedar wood oil, peppermint oil, Wintergreen oil and / or orris concrete), surfactants (e.g., ethanolamine dodecyl sulfate (K12 EA), sodium dodecyl sulfate (AS), potassium dodecyl phosphate(PK), linear sodium alkyl benzene sulfonate (LAS), sodium oleoyl amino fatty acid, sodium N-oleoyl-N-methyl taurinate, sodium salt a-sulfo fatty acid methyl ester (MES), sodium stearate, sodium oleate, ammonium oleate, glycerol monooleate, potassium oleate, potassium stearate, zinc stearate, magnesium stearate, polyoxyethylene fatty alcohol sodium sulfate (AES), ethoxylated alkyl ester sulfo succinate, alkylbenzene sulfonic acid, sodium alkyl sulfonate, a-alkene-sulfonate (AOS), secondary alkane sulfonate (SAS), sodium dialkyl ester sulfonsuccinate, N-acyl glutamate (AGA), triethanolamine polyoxyethylene fatty alcohol sulfate (TA-40), sulfonated caster oil, Span-20, 40, 60, 65, 80, Tween-20, 40, 60, 65, 80, secondary alcohol polyoxyethylene ether (JFC), fatty alcohol polyoxyethylene(3) ether (AE03), fatty alcohol polyethoxylate(7) ether (AE07), fatty alcohol polyoxyethylene(9) ether (AE09), fatty alcohol polyethoxylate(IO) ether (AEO10), fatty alcohol Polyoxyethylene(15) ether (AE015), fatty acid alkanol amide, fatty acid polyoxyethylene(IO) ester, glyceryl oleate, glycerol trioleate, glyceryl stearate, alkylphenol polyoxyethylene(IO) ether, coco fatty diethanol amide, coco fatty monoethanol amide, caster oil polyoxyethylene ether, ethoxylated metluyl glucoside sesquistearate (MSE), methyl glucoside sesquistearate, sucrose fatty acid ester, polyoxyethylene-polyoxypropylene glycols, polyoxyethylene alkylamide, dodecyl dimethyl betaine, alkyl dimethyl betaine, coco amino propyl betaine, carboxylate- type imidazoline ampholytic surfactant, carbomer, ethoxylated lanoilu, ethoxylated lanoilu alcohol, lanolin fatty acid, iso-propyl lanolate, liquid lanolin, and lecithin), synergists (e.g., alkyl glucoside, lactic acid, methyl silicone oil, isopropyl alcohol, ethanol, oleic acid, polyoxyethylene alkyl ether, alkyl sulfates, dialkyl succinate, alkyl amide taurine salt, fatty alcohol polyoxyethylene ether sulfonate, fatty alcohol ethoxylates, lactic acid ethyl ester, phenethyl propionate, polyglyceryl stearate, sodium polyacrylate, calcium lignin sulfonate, dialkyl succinate sulfonate, ethylene glycol monoether, amyl acetate, 2-butanone, n-butyl alcohol, dibutyl phthalate and n-butyl acetate), terpenes and / or terpenoids.

[0067] In exemplary embodiments, the composition contains one or more additives in a weight percentage, based on the total weight of the composition, of about 1wt%, about 5wt%, about 10 wt%, about 20 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 70 wt%, about 80 wt% or any weight percentage or weight percentage range falling within the range of 1 wt% to 80 wt%.

[0068] The insecticidal composition can be in the form of an emulsion, a powder, a water-based spray or an aerosol.

[0069] In exemplary embodiments, the composition contains the at least one biobased carbamate in a weight percentage, based on the total weight of the composition, of about 1wt%, about 5wt%, about 10 wt%, about 20 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 70 wt%, about 80 wt% or any weight percentage or weight percentage range falling within the range of 1 wt% to 80 wt%.

[0070] Examples

[0071] The present disclosure will be described in more detail with reference to the following Examples, which shows exemplary embodiments in accordance with the present disclosure. The present disclosure is not limited to these exemplary embodiments.

[0072] Example 1 : Bio-based Insecticide Production from Biomass Derived Furfural and Vanillin

[0073] I. Materials and Methods of Example 1

[0074] Materials

[0075] Methylene chloride, furfural, vanillin, furfurylamine, anhydrous sodium sulfate, anhydrous dimethyl carbonate, liquid ammonia, deuterated solvents de- DMSO, and CDCh were all used as received. Supported metal oxides and metal triflate catalysts were all purchased from Sigma Aldrich. Metal oxides were reduced at 300 °C for 3 hours at a ramp rate of 10 °C / min under 100 cm3 / min 10% hydrogen / helium flow. Vanillylamine was purchased from MedChem.

[0076] Catalytic Reaction and Product Analysis

[0077] The reductive amination reactions were conducted in 50 mL Parr reactors. The reactants and the catalyst were placed in a glass liner with a magnetic stir bar. After loading the glass liner in the Parr reactor, the reactor was closed, purged three times with nitrogen, twice with hydrogen, and then pressurized to the desired hydrogen pressure. After a designated reaction time, the reactor was cooled in an ice bath, depressurized, and opened. Products were extracted using methylene chloride with a gravity separation funnel.

[0078] For the next carbonylation step, reactions were conducted in 10 mL glass vials heated in an aluminum heating block with controlled stirring. Scale-up reactions were conducted in 50 mL round bottom flasks heated in an oil bath and connected to a reflux condenser. Temperature and stirring rate were maintained at 80 °C and 800 rpm, respectively. After reacting for a set amount of time, the reaction vials were removed from the heating block and cooled to room temperature. The products and remaining reactants were identified and quantified via a gas chromatogram mass spectrometer (GC-MS) equipped with a DB-5 column and a gas chromatogram with a flame ionization detector (GC-FID) equipped with an HP-1 column. For quantification, the effective carbon number method (ECN) was used, with eicosane as the internal standard (J. T. Scanlon, D. E. Willis, J. Chromatogr. Sci., 1985, 23, 333-340). Calibration curves were developed whenever compounds were either commercially available, such as furfural, vanillin, furfurylamine, vanillylamine or were purified in large quantities, for example methyl (2-furylmethyl)carbamate (FC) and methyl(4-hydroxy-3- methoxybenzyl) carbamate (VC).

[0079] Reductive Amination

[0080] Upon completion of the reductive amination reactions, the Rh / A Os catalyst was recovered through vacuum filtration. The collected catalyst was washed multiple times with DI (de-ionized) water and re-used for subsequent reactions.

[0081] Carbonylation

[0082] Upon completion of the carbonylation reaction, dimethyl carbonate was removed through rotary evaporation and the residue was dissolved in 20 mL of methylene chloride. The organic solution was subjected to three washes with 20 mL of DI water, the aqueous phases were collected, and the water was distilled off to recover the lanthanum triflate catalyst. The triflate was washed with methylene chloride to remove residual organic compounds and air-dried before re-use.

[0083] Product Purification and Characterization

[0084] Upon completion of the carbonylation reaction, the organic solution was diluted with methylene chloride and subjected to multiple washes with 2% citric acid to purify the amine and extract any remaining triflate catalyst in the organic solution. The organic phase was then dried over anhydrous sodium sulfate, and the pure carbamate was obtained via rotary evaporation.

[0085] The carbamate products were characterized to determine purity and molecular weight. Liquid chromatography -mass spectrometry (LC-MS) and electron spray ionizations mass spectrometry (ESI-MS) data was obtained from the Mass Spectrometry Facility at the University of Delaware. All reported results were done in duplicates.

[0086] Lethal Concentration Studies

[0087] The median lethal concentration (LCso) of chemicals was measured in adult lesser mealworm beetles (Alphitobius diaperinus) through vial bioassays. Adult lesser mealworm beetles are a common pest worldwide and often used as a test species for commercial insecticides. The beetles were sourced from a UD Agricultural Entomology Lab colony collected from a Delaware broiler house and housed in a controlled growth chamber (kept at 25°C, -60% humidity, and in darkness). The colony was sustained on chicken layer pellets, supplemented with apple and carrot, and with Styrofoam blocks provided as pupation substrate. Preliminary screenings determined lethal concentration ranges for each chemical, achieved in glass vials by evaporating acetone-based insecticide dilutions. Five replicates per concentration and acetone-only controls were set up for each chemical. Mortality and morbidity assessments were conducted after 48-hour exposures. Statistical analysis involved probit regression, excluding vials displaying 0% or 100% mortality to avoid influences of false endpoints. Adjustments for heterogeneity factors were made based on chi-square goodness-of-fit test results.

[0088] Computational Ecotoxicity Simulations

[0089] The Toxicity Estimation Software Tool (TEST), developed by EPA, was used to estimate the lethal dose for 50% death (LDso) for mammals and lethal concentration (LCso)for aquatic species. The species considered were a rat, fathead minnow (fish), and daphnia magna (plankton). TEST is a peer-reviewed tool using QSAR (Quantitative Structure-Activity Relationship) to estimate chemical toxicity based on molecular descriptors, like molecular weight and octanol-water partition coefficient (log(Kow)). TEST has been trained on datasets from ECOTOX, which contain various aliphatic and aromatic carbamates, amines, and amides structurally similar to the carbamates analyzed in this Example. TEST predictions were supplemented by ECOSAR (J. T. R. Tracy Wright et al., “Operation manual for the ecolological Structure-Activity Relationship Model (ECOSAR) Class Program, 2022; and H. Sanderson, et al., Toxicol. Lett., 2003, 144, 383-395). ECOSAR estimates acute toxicity of aquatic species using the Meyer-Overton relationship, applied to chemicals within a structurally similar class. ECOSAR has been optimized for molecules with a logP less than 5 and molecular weight less than 1000 g / mol. Biotransformer was used to predict small molecule metabolism in human tissues, gut, and the environment.

[0090] Hydrolysis Degradation Experiments

[0091] Hydrolysis was done by dissolving 100 mg of the carbamate compounds in methanol and adding the solution to an alkaline buffer. The organic phase of these solutions was extracted with ethyl acetate after 24 hours and analyzed using GC- MS.

[0092] ASPEN Simulations

[0093] The capital and operating costs are estimated using the Aspen Process Economic Analyzer (APEA) V12.0 (“Aspen Plus V12,” DOI 10.1007 / BF00447266, 2023). The economic evaluation was conducted based on the discounted cash flow analysis. The number of years for analysis was 20 and the payout time was 10. The active ingredient's minimum selling price (MSP) was determined such that the net present value (NPV) was zero at payout time. The cost of catalyst recovery was not considered.

[0094] II. Results of Example 1 Experiments

[0095] Reductive Amination of Vanillin

[0096] The selective reductive amination for vanillin was challenging due to its propensity to dimerize. FIG. 1 illustrates a reaction network for the reductive amination for vanillin. Creosol (a byproduct) results from the hydrodeoxygenation of vanillin. Reductive amination progressed through a Schiff base-type imine intermediate from the interaction of ammonia and the aldehyde group. The Schiff base-type imine intermediate then underwent a hydrogenation to vanillylamine or a secondary amine.

[0097] The metal catalyst and support strongly affected the selectivity of the reductive amination. The initial conditions and catalysts were adopted from recent literature. As shown in FIG. 2(a), amalgams, like Raney nickel catalysts, lead to the secondary amine (BVA) while no reduced products (creosol or the primary amine) formed. Strong reducing metals, such as Pd and Ru on carbon, produced exclusively creosol. Rh / Al2O3 exhibited the highest selectivity to the desired vanillylamine (a yield of 34.6%). Ru / C resulted in a vanillylamine yield of 10.4%.

[0098] The maximum vanillylamine yield was obtained at 40 bar H2 in 30 minutes at a temperature of 90°C. Temperature profoundly affected selectivity of the reductive amination reaction (Error! Reference source not found. (b)). At a temperature of 100°C, the carbonyl group in vanillin was reduced, thereby producing creosol in high yield. Intriguingly, selectivity shifted to dimerized products below 80°C. The hydrogen pressure and reaction time were also optimized (FIG. 2(c) and FIG. 2(d)). Reductive Amination of Furfural

[0099] The reductive amination of furfural proceeded via the same mechanism shown in FIG. 3. A hydrogen pressure of 40 bar (FIG. 4(a)), a temperature of 100 °C (FIG. 4(b)), with a reaction time of 30 minutes, gave a 93% amine yield (FIG. 4(c)). Lower temperatures favored the secondary amine (60% and 30% selectivity at 60°C and 80°C, respectively). Longer reaction times promoted ringhydrogenation, consistent with prior work on ring hydrogenation of furfural and 5- hydroxymethyl furfural (HMF) over Ru and Rh catalysts.

[0100] Upon completion of the reaction, the Rh / AhOs was recovered through vacuum filtration. The collected catalyst was washed multiple times with DI water and re-used for the subsequent reaction. The recyclability data, given in FIG. 5, indicates a slight change in product distribution but the overall product yield remained the same.

[0101] Carbonylation of Furfurylamine

[0102] Carbonylation was performed on furfurylamine in the presence of various metal triflates. The mechanism involving dimethyl carbonate (DMC) activation has been extensively studied, and involves the coordination of the metal ion with the carbonyl oxygen to facilitate the attack of the amine group on the positively charged carbonyl carbon shown in FIG. 6. This leads to the formation of carbamate ester products and the generation of methanol as a stoichiometric byproduct FIG. 7. The reaction network for this carbonylation with furfurylamine is also given in FIG. 7. The activity of metal triflates correlates with their Lewis acidity, as shown in FIG. 8, with high conversions of furfurylamine to FC for La (82%), Sc (81 %), and Zn (78%). Byproducts included tris(furan-2-ylmethyl)amine (TA), N-methyl furfurylamine (MFA), and the 1-(2-furyl)-N-(2-furylmethyl)methanimine (DA).

[0103] Optimization of the catalyst / amine ratio and the DMC / amine ratio was conducted with La(OTf)s. Higher DMC / amine ratios increased the activity and selectivity to FC (FIG. 9). The conversion of furfurylamine increased from 61% to 82% when the DMC / amine ratio was doubled. A possible explanation for this increase is that excess DMC allowed for better mixing, thereby increasing conversion. Higher catalyst loadings increased furfurylamine conversion and selectivity to the primary carbamate (FIG. 10). The highest yield of FC (95%) was achieved at a DMC / amine / catalyst ratio of 10 / 1 / 0.1 . Time-dependent studies (FIG. 11) provided insight into the mechanism of the carbonylation of furfurylamine, illustrated in FIG. 8. Methylation of furfurylamine was found to occur after significant amounts of FC and methanol were produced stoichiometrically (0% yield at 2 h, 3% yield at 8 hours). This indicates that methylation was due to the methanol generated in situ. Triflates can catalyze methylation by coordinating with amine groups. Coordination of the metal with the amine group and concomitant dehydrogenation of FA and DA could also lead to the formation of triamines. The decrease in the secondary imine yield at longer times (3% at 4 hours and 0.5% at 8 hours) and the concurrent increase in triamine yield (0 at 4 hours to 2% at 8 hours) also indicated that these byproducts are produced sequentially.

[0104] Carbonylation of Vanillylamine

[0105] Carbonylation of vanillylamine gave a modest yield to methyl(4- hydroxy-3-methoxybenzyl) carbamate (VC) (52% shown in FIG. 12) possibly due to polymerization and dimerization of vanillylamine.

[0106] Insecticidal activity

[0107] The performance of the synthesized biobased insecticides (FC and VC) were compared to carbofuran, one of the most toxic synthetic carbamate insecticides in use (Table 1).

[0108] Table 1 : Probit analysis results for adult Alphitobius diaperinus exposed in vial bioassays to carbofuran (CF), methyl (2-furylmethyl)carbamate (FC), and methyl (4-hydroxy-3-methoxybenzyl) carbamate (VC). Chemica .l Pooled number of beetles for Slope LCso (95% Cl) ana .lysis (SE) (ng / cm2.

[0109] CF 524 0.49 (0.07) 251 ,258 (106,755-560,330)

[0110] FC 210 2.61 (0.45) 254,226 (160,787-518,110)

[0111] VC 375 5.25 (0.84) 6,660,622 (5,806,798 -9,961,100) The median lethal concentration (LCso) for FC was equivalent to the LCso for carbofuran, with confidence intervals broadly overlapping (FIG. 13). The LCso for VC was two orders of magnitude higher than those for carbofuran and FC, thereby indicating lower toxicity. The comparable performance of FC with one of the most toxic synthetic insecticides, on the other hand, is encouraging and signifies that grafting biomass derived monomers with molecular precision has the potential to replicate toxicity of commercial insecticides.

[0112] Ecotoxicity evaluation

[0113] A major environmental concern with the conventional pesticides is the potential to bioaccumulate and threaten the ecosystem. Carbofuran is highly toxic to birds, mammals, marine fish, and freshwater invertebrates on an acute basis. Other carbamates, such as aldicarb and carbaryl, threaten aquatic species such as snakehead fish and salmon, potentially killing thousands in affected water bodies. Carbamate insecticides are acetylcholinesterase (AChE) inhibitors (Mode of action group 1 A) and, despite their potent insecticidal activity, are under stringent regulations due to their non-specificity.

[0114] Therefore, examination of the biobased insecticides FC and VC was evaluated to determine their ecotoxicities. The aquatic and mammalian toxicity of FC and VC was predicted using the peer-reviewed TEST software and compared with the commercial carbamates (FIG. 14, FIG. 15 and FIG. 16). The raw toxicity data for three non-target species: rats (Rattus rattusa, a mammal), fathead minnows (Pimephales promelas, a freshwater fish), and Daphnia magna (a planktonic crustacean) is given in Table.

[0115] Table 2: Raw data of the ecological risks of insecticidal active ingredients simulated using TEST

[0116]

[0117] Compared to the available experimental toxicity data for all three species, it was discovered that at the log scale, TEST has a mean percentage error below 15% (Table 3Error! Reference source not found.), indicating its accuracy for the subset of compounds selected.

[0118] Table 3: Mean percentage error of TEST for the compounds screened.

[0119] FC has one of the highest LDso for rats and the highest LCso for fathead minnows indicating that it is less toxic than conventional carbamates. Carbofuran's (CF) ecotoxicity is an order of magnitude higher than FC in all three categories despite having similar toxicity toward the target pest. EPA’s classification for pesticide toxicity to humans and aquatic species ranges from acutely toxic (category I) to non-toxic (category IV). FC’s predicted oral median lethal dose for rats, 1160 mg / kg, and LCso of 83 mg / L place it in toxicity category III (500-5000 mg / kg oral and 10-100 mg / L fathead minnow). This corresponds to a slightly toxic label, while most conventional pesticides carry acute toxicity designations (category I). These results indicate that FC is an ecologically safer insecticide than many commercial pesticides currently on the market. VC has a predicted oral LDso of 175 mg / kg and LCso of (11 mg / L) placing it in category II (moderately toxic) for mammals and borderline category III for fish. These results indicate that FC is a potent but also less ecologically toxic insecticide and signify the sustainable impact these biomass-derived compounds can bring to crop protection methods.

[0120] Next, the ecotoxicity of the biobased insecticides prepared according to the Example (FC and VC) were compared to several biopesticide active ingredients with aromatic and heterocyclic groups that are registered with the EPA. FC displayed lower toxicity towards fish (FIG. 17), higher toxicity towards mammals (FIG. 18) and comparable toxicity towards Daphnia magna (FIG. 19). VC displayed similarly high toxicity to the commercial carbamates. The higher toxicity towards mammals could be due to the carbamate functional group. However, despite the presence of the carbamate functionality, FC emerges as one of the less toxic compounds for fathead minnows.

[0121] Specific functional groups can impact the toxicity of pesticide end-life products. Incorporating electron-donating groups, such as ether or amines, is particularly advantageous to reduce the molecule's lipophilicity and enhance its potential for photodegradation. Specifically, subsituting the nitro groups (electron withdrawing) with amines (electron donating) on 2-methyl-4,6-dinitrophenol (DNP) remarkably increased its photodegradation potential and decreased its bioavailability, shifting it to a lower risk chemical. The results of the studies conducted in this Example suggest that similar ecological benefits can occur by substituting unreactive benzene cores found in many commercial pesticides with an electron-dense, five-membered ring containing an oxygen heteroatom.

[0122] FC’s low bioavailability, attributed to a low octanol water partition coefficient (Kow), counteracted the potential toxic effects of the carbamate group in fish. It is worth noting that bioavailability is not deemed significant in the toxicity simulations for mammals, as the model focuses on the oral dosage of the active ingredient rather than the diffusion of the compound into nearby organisms.

[0123] The Ghose-Crippen octanol / water partition coefficient (Kow) was predicted using TEST. Kow is a useful index for quantifying insecticides aquatic toxicity since it indicates whether the compound endures in the aqueous phase, such as the water body into which it is introduced, or infiltrates into organisms. A lower Kowimplies a reduced likelihood of a compound diffusing into aquatic species, and thus a reduced ecotoxicity. Conventional insecticides derived from benzene-based materials have a higher Kow, the majority of them have log(Kow) values >2. FC, on the other hand, has a Kow of 1 , representing an order of magnitude difference. The increased dipole moment and electron density in furans, compared with benzene rings, due to the oxygen heteroatom, resulted in a lower Kowthan commercial pesticides, thereby indicating a lower aquatic toxicity. Consequently, the favorable electronic properties of the furan ring are crucial contributors to the low ecotoxicity of FC. Another important molecular descriptor for ecotoxicity is a compound’s molar refractivity. We thus also predicted the Ghose Crippen molar refractivity (AMR) for the different compounds, shown in Table 2. A high AMR correlates to higher ecotoxicity. To corroborate the findings from TEST, the aquatic toxicity of VC and FC to fish and green algae was evaluated using ECOSAR (Ecological Structure Activity Relationships). The tabulated values are shown in Table 4.

[0124] Table 4: Tabulated ECOSAR LCso predictions with the appropriate chemical class

[0125]

[0126] FC (109.6 mg / L) and VC (112.5 mg / L) are shown to have higher LCso’s for fish compared to all the industrial carbamates and all but two biopesticides. For green algae, FC (0.95 mg / L) and VC (0.45 mg / L) were safer than the majority of industrial carbamates. Interestingly, all the carbamate molecules had low (<2.5 mg / ml) ECso (Effective Concentration) values, while the majority of biopesticides were safer (>10 mg / ml), indicating that green algae is particularly sensitive to the carbamate functional groups.

[0127] These results clearly distinguish FC from conventional carbamate insecticides and show that its risk to aquatic environments is low, even when compared with the inherently safer biopesticides. These results also indicate that similar biomass-based insecticides can alleviate current ecotoxicity concerns associated with the carbamate class of insecticides.

[0128] Extending the Synthetic Scope

[0129] The array of bio-derived furans, diols, and aromatics that can be transformed into amines underscores the broad scope of the synthesis method used in this Example and those disclosed herein. To showcase this versatility, six carbamate molecules have been synthesized from other biomass-derived monomers. Table 5 details their structures, along with the achieved yield. Table 5: Different carbamates synthesized using the methodology of Example 1 . ructure C „ Amine „ .

[0130] Compound Acronym St o Carbamate

[0131] ,nve .r.s. i .on . Y..ie .ld. . ... .

[0132] (mol%) ( 'mol%) '

[0133] Methyl (tetrahydro-2- furanylmethyl)carbamate TH FC 100 91

[0134] Methyl (6- hydroxyhexyl)carbamate HOHC 100 87

[0135] Methyl (4- hydroxybenzyl)carbamate PC* 100 32

[0136] Methyl (2-

[0137] TC 86 82 thienylmethyl)carbamate ,

[0138] T-T HU

[0139] 0

[0140] Methyl [(5-methyl-2- o. ...«, J! furyl)methyl]carbamate MFC "T jT N o' 97 88

[0141] / 0

[0142] Methyl (3,4,5- trimethoxybenzyl)carbamate MTBC 100 67

[0143] The TC monomer was less reactive than furan-based amines with similar high (>95%) conversions. PC (32% carbamate yield) was more susceptible to dimerization than VC (52% carbamate yield) and MTBC (67% carbamate yield), resulting in lower yields of the carbamate (36%). The ecotoxicity predictions of these new compounds are shown in Table 6.

[0144] Table 6: Ecotoxicity predictions for the different biobased carbamates synthesized Structural modifications to the furan-based compounds THFC, MFC, and TC influenced the LC50 toward fathead minnows. THFC showed an unprecedented lack of toxicity toward fathead minnows (162 mg / L = category IV), whereas MFC and TC were more ecotoxic (56 mg / L and 46 mg / L, respectively). The structural modifications significantly impacted Kow, as shown in Table 6. MFC and TC had higher Kowvalues and, interestingly, THFC had a Kowlower than FC by close to a factor of 3. Adding a methyl chain to the furan ring decreased the water solubility of MFC and substituting the oxygen heteroatom with sulfur reduced the polarity as sulfur is less electronegative than oxygen. The solubility of THFC can be explained by the localization of the lone pair on the oxygen heteroatom. The resonance of the unsaturated furan ring delocalizes the negative charge, reducing the overall polarity of the molecule.

[0145] PC and MTBC, the structural analogues of VC, exhibited an interesting trend in predicted ecotoxicity. According to the predictions, PC is safer since its LCso and LD50 to fish are thrice that of VC (30 mg / L vs 11 mg / L and 524 mg / kg vs 175 mg / kg). These predictions change the category of this active ingredient to category III (524 mg / kg) for mammals and firmly in category III (30 mg / L) for fish. Methoxy and alcohol groups are not predicted to significantly impact log(Kow) but could increase AMR. The addition of methoxy groups can clearly increase the AMR for VC and MTBC, resulting in higher ecotoxicities.

[0146] These observations are significant as they underscore favorable ecological property engineering by tuning the substituents and heteroatom of the furan and phenolic ring to impact Kowand the AMR of pesticide molecules.

[0147] Fate of Degradation Products

[0148] With exciting potency and ecotoxicity data for FC and VC, the fate of the end-life environmental degradation products was next evaluated since the end-life products of industrial carbamates can often be harmful. As shown in FIG. 20, the carbofuran undergoes ester group hydrolysis, resulting in an alkyl amine, CO2, and an organic residue. To evaluate the degradation of VC, FC and carbofuran, the alkaline hydrolysis was conducted using different pH buffers, and the metabolites were extracted with ethyl acetate and analyzed. Carbofuran completely hydrolyzed to phenol hydro furan after 12 hours in a buffer of pH 10 (FIG. 21 (a)). Surprisingly, FC remained stable and persisted even at a higher pH of 12. This unexpected stability could be attributed to the orientation of the carbamate group. That is, the ester linkage in carbofuran is connected to the aromatic ring, thereby making the ester groups highly susceptible to hydrolysis. In contrast, the -NH group in FC and VC is connected to the furan or aromatic ring, thereby providing hydrolysis resistance. Due to their respective amines or aromatic moieties (FIG. 21 (b)), it is speculated that FC and VC degrade in a manner similar to Fenoxycarb, a carbamate insecticide that mimics a juvenile hormone (Group 7) and is used to disrupt insect development. Fenoxycarb's carbamate group has a similar orientation to FC and VC, and Fenoxycarb has been shown to degrade via photolysis. The corresponding amine for FC and VC was confirmed as the main degradation product using biotransformer. The degradation products were also assessed with TEST as shown in Table 7.

[0149] Table 7: Ecotoxicity predictions for the degradation products of FC and VC.

[0150] The respective amines were predicted to be less toxic to Daphnia magna and the fathead minnow. Furfurylamine was also predicted to be more toxic toward mammals than FC.

[0151] Technoeconomic Analysis

[0152] Using Aspen 12's economic analyzer, the technoeconomics of FC were evaluated. The plant's capacity was assumed to be 1000 tons / yr, approximately 20% of worldwide carbofuran production. The breakdown of capital and operating costs, along with the costs of each component needed to produce FC, are provided in Tables 8 and 9.

[0153] Table 8: Breakdown of capital and operating costs.

[0154] Table 9: Cost per component

[0155] A minimum selling price (MSP) of the active ingredient is predicted at 11 .14 $ / kg, a third of carbofuran's price of 34 $ / kg, and half of carbaryl's selling price of 23

[0156] $ / kg. This cost advantage can be attributed to using inexpensive commodity chemicals, including furfural, ammonia, and dimethyl carbonate, for synthesizing a high-value active ingredient. Furthermore, the process involves only two synthesis steps and easy purification methods, while conventional carbaryl and carbofuran synthesis involves four to five steps with a cost associated with separation in each step.

[0157] Principles of Green Chemistry

[0158] Table 10 highlights the 8 green chemistry principles that were satisfied in the Example.

[0159] Table 10: Principles of Green Chemistry

[0160] The synthesis method used to produce FC demonstrated a high atom economy of 74%, meeting criterion 2. The ecotoxicity analysis data shown in Tables 2 and 4 satisfy criterion 3. The ecotoxicity of the reagents utilized in the synthesis of this Example, such as dimethyl carbonate and furfurylamine, and the intermediates of carbofuran, such as 2,2 dimethyl-7-hydroxycoumaran and methyl isocyanate, are shown in Table 11 . Table 11 : Ecotoxicity predictions for the reagents used in the synthesis of FC and carbofuran

[0161] The latter reagents have lower LDso and LCso values to mammals and aquatic life. This demonstrates that the synthesis in this Example utilizes safer chemicals and solvents, satisfying criteria 4 and 5. Furfural is a biomass-derived platform chemical, meeting criterion 7. The synthesis also utilizes recyclable catalysts and includes no protection groups, satisfying criteria 8 and 9. Finally, methyl isocyanate is a highly volatile chemical, responsible for the worst industrial chemical disasters. Eliminating the use of methyl isocyanate in the synthesis achieves the goal of inherently safer chemistry for accident prevention.

[0162] III. Conclusion of Example 1

[0163] Sustainably sourced pesticides are needed to reduce reliance on synthetic pesticides derived from fossil fuels at an annual volume of 5.6 billion pounds. Emerging biopesticides are projected to be the future of crop protection but are limited by short supply. In this context, Example 1 introduced a synthesis of structurally similar insecticidal active ingredients with molecular precision from biomass resources. This synthesis combines two well-established industrial chemistries, reductive amination and carbonylation, to upgrade commercially available biobased platform molecules, furfural, and vanillin, to carbamate functionalized insecticides, FC and VC, satisfying 8 out of 12 criteria in green chemistry synthesis. The conditions were optimized to achieve -95% yield of furfurylamine and FC in the reductive amination and carbonylation steps. The insecticidal activity evaluation against a known pest, lesser mealworm beetles (Alphitobius diaperinus), showed that FC has comparable potency to the widely used and highly toxic commercial insecticide, carbofuran. VC was less effective and can be a potential candidate as herbicide or plant growth regulator. Ecotoxicity predictions using the EPA developed software TEST revealed that the synthesized biobased compounds are in ecotoxicity category III (minimal ecotoxicity) and thus considerably safer than most conventional pesticides. The predictions also show that FC is safer than most biopesticide active ingredients toward fathead minnows’ aquatic species. Octanol and water partition coefficient predictions indicate that these biobased insecticides have lower potential for bioaccumulation in aquatic species. The lower ecotoxicity for FC can be attributed to the electronic properties of its furan ring. By modifying the ring substituents, the ecotoxicity of these biobased insecticides can be tuned. Finally, technoeconomic analysis showcases the economic viability for producing FC. Overall, the data gathered from performing the experiments of this Example provide a foundation for biomass-derived, environmentally safer pesticides that could be transformative for crop protection.

[0164] It will be appreciated by those skilled in the art that the present disclosure can be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The presently disclosed embodiments are therefore considered in all respects to be illustrative and not restricted. The scope of the disclosure is indicated by the appended claims rather than the foregoing description and all changes that come within the meaning and range and equivalence thereof are intended to be embraced therein.

Claims

CLAIMS:1 . A process for preparing a bio-based carbamate insecticide comprising: performing a reductive amination reaction on an aldehyde to produce an amine product; and subjecting the amine product to a carbonylation reaction to produce the bio-based carbamate insecticide.

2. The process of claim 1 , wherein the bio-based carbamate insecticide is either a compound of Formula (I):Formula (I), wherein:Ri is H,R2is H,R3is H, -CH3or -CH2OH, and R4 is O, S or NH; a compound of Formula (II):Formula (II), wherein:R1 is H,R2is H,R3is H, -CHs or -CH2OH, andR4 is O, S or NH; a compound of Formula (III)Formula (III), wherein:Rs is -OCH3, -OH or H,Re is -OCH3, -OH or H, and R7 is -OCH3, OH or H; or a compound with a structure of:

3. The process of claims 1 or 2, wherein the aldehyde is selected from:

4. The process of any one of the preceding claims, wherein the performing of the reductive amination reaction comprises reacting the aldehyde with ammonia under a H2 pressure ranging from 30 bar to 60 bar.

5. The process of any one of the preceding claims, wherein the reductive amination reaction occurs for about 30 minutes to about 120 minutes.

6. The process of any one of the preceding claims, wherein the reductive amination reaction is performed at a temperature ranging from 80°C to 100°C.

7. The process of any one of the preceding claims, wherein the reductive amination reaction is performed in a presence of a first catalyst, that catalyst being selected from Rh / AhOs, Pd / C, Ru / C, Ru / ZrO2, Raney Nickel, Rh / C or Pt / C.

8. The process of any one of the preceding claims, wherein the subjecting of the amine product to the carbonylation reaction comprises reacting the amine product in a presence of a metal triflate catalyst in dimethyl carbonate.

9. The process of claim 8, wherein the metal triflate catalyst is ytterbium triflate, lanthanum triflate, scandium triflate or zinc triflate.

10. The process of claim 8, wherein dimethyl carbonate is present in the carbonylation reaction in a concentration ranging from 20 mmol to 60 mmol.11 . The process of any one of the preceding claims, wherein the carbonylation reaction occurs for about 8 to about 16 hours.

12. The process of any one of the preceding claims, wherein the carbonylation reaction comprises reacting the amine product with dimethyl carbonate (DMC) and a catalyst in a DMC / amine / catalyst ratio of 10:1 :0.1 .

13. The process of any one of the preceding claims, wherein the reductive amination reaction produces the amine product in a yield ranging from about 85% to about 100%.

14. The process of any one of the preceding claims, wherein the carbonylation reaction produces the bio-based carbamate insecticide in a yield ranging from 60% to about 95%.

15. The process of any one of the preceding claims, the process comprising: isolating the aldehyde from a renewable resource containing lignosulfonates, kraft and / or alkali lignin.

16. The process of claim 15, wherein the isolating of the aldehyde from the renewable resource comprises:depolymerizing the lignosulfonates to produce a reaction mixture containing the aldehydes, and precipitating the aldehydes out of the reaction mixture.

17. The process of claim 15, wherein the renewable resource is cellulosic biomass.

18. An insecticidal composition comprising a bio-based carbamate produced from the process of any one of claims 1 to 17.

19. The insecticidal composition of claim 17, wherein the composition has an LCso against adult Alphitobius diaperinus of at least 6,660,622 ng / cm3.

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