Alternatively sourced surfactants and related methods

Abstract

The present disclosure generally relates to castor-derived and shea-derived surfactant compounds which may be utilized as surfactants in a variety of personal care and general cleaning compositions. Methods of preparing surfactant compounds are also provided.

Description

ALTERNATIVELY SOURCED SURFACTANTS AND RELATED METHODSBACKGROUND OF THE DISCLOSURE

[0001] The surfactant market, particularly in personal care, is dominated by materials prepared from coconut and coconut palm-based products (e.g., sodium lauryl sulfate (SLS), sodium lauryl ether sulfate (SLES)). Such coconut and coconut palm-based surfactants have been industry standards for years and are widely used in various personal care applications (e.g., shampoos, conditioners, body wash, face wash). With recent consumer trend towards sulfate free products which are environmentally friendly as well as sustainable and responsibly sourced, there exists a need for suitable surfactant alternatives which provide the same highly desirable formulation performance characteristics and satisfy consumer demands / trends.SUMMARY OF THE DISCLOSURE

[0002] The present disclosure generally relates surfactants derived from alternatives to coconut and coconut palm. More particularly, the surfactants disclosed herein provide similar performance characteristics to the lauryl and sulfate-based surfactants. The surfactants disclosed herein may be sulfate free or substantially free of sulfates. The surfactant provided herein may be derived from sustainable sources that can be grown and reasonably sourced from various countries around the world.

[0003] According to one aspect, the surfactants provided herein may be castor-based or shea-based. Such surfactant compounds may include a variety of head groups and an alkyl linker of varying carbon length between the head group and a lipophilic tail. The lipophilic tail optionally includes at least one or more degrees of saturation.

[0004] A castor-based surfactant compound of Formula (I) is provided:Formula (I) wherein: n is 0, 1 , 2, 3 or 4;x is 3, 4, 5 or 6;L is a Ci-Cs linker group that is either fully saturated or has one or more degrees of unsaturation;Ri is H, OH, or CH3;Rz is C1-C12 alkyl or C1-C12 alkene;R3 is NH, NCH3, O, or R3 is N and together with R4 forms an optionally substituted heterocyclic

[0005] According to one embodiment, R2 is Ce-alkyL According to one embodiment, the optionally substituted heterocyclic ring includes

[0006] According to one embodiment, L is a Ci-Cs linker group having one or more degrees of unsaturation. According to one embodiment, L is a Ci-Cs linker group having one or more degrees of unsaturation, R1 is H, and R2 is CH3. According to one embodiment, L is a C2-C6 linker group having one or more degrees of unsaturation. According to one embodiment, L is a C2-C6 linker group having one or more degrees of unsaturation, R1 is H, and R2 is CH3.

[0007] According to one embodiment, L is a Ci-Cs linker group that is fully saturated. According to one embodiment, L is a Ci-Cs linker group that is fully saturated and R1 is H.

[0008] According to one embodiment, the castor-based surfactant compound includes one or more of (R,Z)-2-((3-(12-hydroxyoctadec-9-enamido)propyl)dimethylammonio)acetate (castor amidopropyl betaine (CAPB)), 2-hydroxy-3-((3-((R,Z)-12-hydroxyoctadec-9- enamido)propyl)dimethylammonio) propane-1 -sulfonate (castor amidopropyl sultaine (CAPS)), (R,Z)-2-((2-(12-hydroxyoctadec-9-enamido)ethyl)dimethylammonio)acetate (castor amidoethyl betaine (CAEB)), (2-hydroxy-3-((2-((R,Z)-12-hydroxyoctadec-9-enamido)ethyl) dimethylammonio)propane-1 -sulfonate (castor amidoethyl sultaine (CAES)), (R,Z)-3-(12- hydroxyoctadec-9-enamido)-N,N,N-trimethylpropan-1 -aminium (castor amidopropyl quat), (R,Z)- 12-hydroxyoctadec-9-enoyl)-L-prolinate (castor prolinate), (R,Z)-12-hydroxyoctadec-9-enoyl)-L- phenylalaninate, (R,Z)-(12-hydroxyoctadec-9-enoyl)glycine, (R,Z)-N-(12-hydroxyoctadec-9- enoyl)-N-methylglycinate, (R,Z)-12-hydroxyoctadec-9-enoyl)-L-glutamate, (R,Z)-2-(12- hydroxyoctadec-9-enamido)ethane-1 -sulfonate (castor taurate), (R,Z)-2-((12-hydroxyoctadec-9- enoyl)oxy)ethane-1 -sulfonate, 2-((9Z,12Z)-octadeca-9,12-dienamido)ethane-1 -sulfonate (linoleoyl taurate), and methyl (9Z,12Z)-octadeca-9,12-dienoate (methyl linoleate).

[0009] A shea-based surfactant compound of Formula (II) is provided:Formula (II) wherein: n is 0, 1 , 2, 3 or 4;Rs is C1-C14 alkyl;According to one embodiment, a shea-based surfactant compound includes one or more of 2- (dimethyl(3-oleamidopropyl)ammonio)acetate (oleoyl amidopropyl betaine), 3-(dimethyl(3- oleamidopropyl)ammonio)-2-hydroxypropane-1 -sulfonate (oleoyl amidopropyl sultaine), and 2-oleamidoethane-1 -sulfonate (oleoyl taurate or shea taurate).

[0010] The present disclosure further provides a personal care composition that includes a surfactant compound of Formula (I) or Formula (II) and one or more acceptable carriers. The personal care composition may be a body wash, hair conditioner, or shampoo. The present disclosure further provides a cleaning composition that includes a surfactant compound of Formula (I) or Formula (II) and one or more acceptable carriers. The cleaning composition may be a bucket dilutable formulation.

[0011] The present disclosure further provides methods of preparing castor-based and shea-based surfactant compounds. The castor-based surfactant compounds provided herein may be prepared from methyl ricinoleate or castor oil utilizing the methods steps described herein. The shea-based surfactant compounds may be prepared from methyl oleate from shea oil or shea butter of a shea tree.

[0012] According to a particular embodiment, a method of preparing castor amidopropyl sultaine (CAPS) is provided that includes the steps of: condensing N,N’-dimethylaminopropylamine (DMAPA) with methyl ricinoleate in the presence of a catalytic amount of sodium methoxide and, optionally, methanol to form castor- DMAPA; adding epichlorohydrin over about 2.5 hours to a 50°C solution of about 40% sodium bisulfite to produce sodium 3-chloro-2-hydroxypropane-1 -sulfonate; and alkylating castor-DMPA with sodium 3-chloro-2-hydroxypropane-1 -sulfonate in a EtOH / H2O mixture at about 80°C to about 90°C to produce castor amidopropyl sultaine (CAPS).

[0013] According to an alternative embodiment, a method of preparing castor amidopropyl sultaine (CAPS) is provided that includes the steps of: condensing N,N’-dimethylaminopropylamine (DMAPA) with castor oil in the presence of a catalytic amount of sodium methoxide and, optionally, methanol to form castor-DMAPA and glycerol; and alkylating castor-DMPA with sodium 3-chloro-2-hydroxypropane-1 -sulfonate in a EtOH / H2O mixture at about 80°C to about 90°C to produce castor amidopropyl sultaine (CAPS).

[0014] A method of preparing shea-based 3-(nonadecanoyloxy)propane-1 ,2-diyl dioleate (methyl oleate) is provided that includes the steps of: mixing shea oil and methanol; adding sodium methanolate to the shea oil and methanol mixture to form a reaction mixture; heating the reaction mixture for form an emulsion having a top phase and bottom phase; andconcentrating the top phase to remove residual methanol and form solid shea-based methyl oleate.

[0015] A method of preparing shea-based 2-oleamidoethane-1 -sulfonate (oleoyl taurate) is provided that includes the steps of: heating a reaction mixture comprising 2-aminoethan-1 -sulfonate, methanol, shea-based methyl oleate, and sodium methanolate; performing a first dilution of the reaction mixture with water; adjusting the pH to about 8; performing a second dilution of the reaction mixture with water; and heating the reaction mixture to form oleoyl taurate.BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 illustrates a method of preparing castor amidopropyl sultaine (CAPS) from methyl ricinoleate according to one embodiment.

[0017] Figure 2 provides an initial process flow diagram for preparing castor amidopropyl sultaine (CAPS) from methyl ricinoleate according to one embodiment.

[0018] Figure 3 illustrates a method of preparing castor amidopropyl sultaine (CAPS) from castor oil according to one embodiment.DETAILED DESCRIPTION

[0019] The present disclosure will now be described more fully hereinafter with reference to exemplary embodiments thereof. These exemplary embodiments are described so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. Indeed, the present disclosure may be embodied in different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements.Definitions

[0020] As used herein, the singular forms “a,” “an,” “the,” include plural referents unless the context clearly dictates otherwise.

[0021] As used herein, the term “alkyl” refers to saturated aliphatic hydrocarbyl groups or chain. The saturated aliphatic hydrocarbyl can be either straight-chained or branched.

[0022] As used herein, the terms “castor-based” and “castor-derived” may be used interchangeably and refer to the starting source material for preparing the surfactant which includes the castor bean as a source of castor oil and methyl ricinoleate.

[0023] As used herein, the term “heterocyclic” refers to mono- or bicyclic compound or group that is saturated or partly unsaturated and contains from 1 to 4 heteroatoms independently selected from oxygen, sulfur, and nitrogen.

[0024] As used herein, the term “optionally substituted” is intended to include both substituted and unsubstituted.

[0025] As used herein, the terms “shea-based” and “shea-derived” may be used interchangeably and refer to the starting source material for preparing the surfactant which includes shea oil, shea butter or methyl oleate from the shea tree.

[0026] As used herein, the terms “sulfate free” and “substantially free of sulfates” means essentially free of sulfate-containing compounds except as otherwise incidentally incorporated as minor components.Surfactants

[0027] A sustainable, non-food source may be utilized to provide a starting material for preparing surfactants. According to a particular embodiment, the sustainable, non-food source includes castor beans. Castor beans are particularly suited for serving as a source material of castor oil or methyl oleate (e.g., 18-carbon fatty acid). Castor beans, for example, are a sustainable source (i.e., not connected to food supply) and can be cultivated in an environmentally friendly and responsible manner. According to one embodiment, glycerol may be present when the castor-based surfactant compound is prepared from castor oil.

[0028] According to one embodiment, the castor-based surfactant compound includes (R,Z)-2-((3-(12-hydroxyoctadec-9-enamido)propyl)dimethylammonio)acetate (castor amidopropyl betaine (CAPB)), 2-hydroxy-3-((3-((R,Z)-12-hydroxyoctadec-9- enamido)propyl)dimethylammonio) propane-1 -sulfonate (castor amidopropyl sultaine (CAPS)), (R,Z)-2-((2-(12-hydroxyoctadec-9-enamido)ethyl)dimethylammonio)acetate (castor amidoethyl betaine (CAEB)), (2-hydroxy-3-((2-((R,Z)-12-hydroxyoctadec-9-enamido)ethyl) dimethylammonio)propane-1 -sulfonate (castor amidoethyl sultaine (CAES)), (R,Z)-3-(12- hydroxyoctadec-9-enamido)-N,N,N-trimethylpropan-1 -aminium (castor amidopropyl quat), (R,Z)- 12-hydroxyoctadec-9-enoyl)-L-prolinate (castor prolinate), (R,Z)-12-hydroxyoctadec-9-enoyl)-L- phenylalaninate, (R,Z)-(12-hydroxyoctadec-9-enoyl)glycine, (R,Z)-N-(12-hydroxyoctadec-9- enoyl)-N-methylglycinate, (R,Z)-12-hydroxyoctadec-9-enoyl)-L-glutamate, (R,Z)-2-(12-hydroxyoctadec-9-enamido)ethane-1 -sulfonate (castor taurate), (R,Z)-2-((12-hydroxyoctadec-9- enoyl)oxy)ethane-1 -sulfonate, 2-((9Z,12Z)-octadeca-9,12-dienamido)ethane-1 -sulfonate (linoleoyl taurate), and methyl (9Z,12Z)-octadeca-9,12-dienoate (methyl linoleate). According to one embodiment, the castor-based surfactant compounds provided herein include the nonionic, cationic, anionic, or amphoteric forms thereof.

[0029] According to one embodiment, the sustainable, non-food source for surfactants provided herein includes shea butter or shea oil. According to a particular embodiment, methyl oleate may be obtained from shea butter or shea oil (from the shea tree) and processed to form a shea-based surfactant compound. According to one embodiment, the shea-based surfactant compound includes 2-(dimethyl(3-oleamidopropyl)ammonio)acetate (oleoyl amidopropyl betaine), 3-(dimethyl(3-oleamidopropyl)ammonio)-2-hydroxypropane-1 -sulfonate (oleoyl amidopropyl sultaine), and 2-oleamidoethane-1 -sulfonate (oleoyl taurate or shea taurate). According to one embodiment, the shea-based surfactant compounds provided herein include the nonionic, cationic, anionic, or amphoteric forms thereof.Methods of Preparation

[0030] A method for preparing castor amidopropyl sultaine (CAPS) from methyl ricinoleate is provided and is set forth in Figure 1 . A process flow diagram for preparing castor amidopropyl sultaine (CAPS) from methyl ricinoleate is provided and is set forth in Figure 2.

[0031] According to one embodiment, the method includes the initial step of condensing N,N'-dimethylaminopropylamine (DMAPA) with methyl ricinoleate in the presence of a catalytic amount of sodium methoxide and, optionally, methanol. Sodium methoxide may be added to the aged reaction mixture and heated to about 80°C to remove methanol and force the reaction to completion. After cessation of methanol generation, the excess DMAPA may be removed under high vacuum at a temperature of from about 110°C to about 120°C to yield (R,Z)-N-(3- (dimethylamino)propyl)-12-hydroxyoctadec-9-enamide (castor-DMAPA)(see Step 1 of Figure 1 ).

[0032] According to one embodiment, the method includes the step of adding epichlorohydrin over about 2.5 hours to a 50°C solution of about 40% sodium bisulfite to produce sodium 3-chloro-2-hydroxypropane-1 -sulfonate. Upon complete addition, the resulting reaction mixture may be stirred at about 50°C for about four hours to afford the desired sodium 3-chloro-2-hydroxypropane-1 -sulfonate (see Step 2 of Figure 1 ; see Figure 2).

[0033] According to one embodiment, the method includes the step of alkylating castor- DMPA with sodium 3-chloro-2-hydroxypropane-1 -sulfonate in a EtOH / H2O mixture at about 80°C to about 120°C to afford the final amphoteric product, castor amidopropyl sultaine (CAPS)(see Step 3 of Figure 1 ; see Figure 2). According to a particular embodiment, ethanol and water may be introduced to castor-DMPA with efficacious stirring. The sodium 3-chloro-2- hydroxypropane-1 -sulfonate may be added to the reactor to afford a thick suspension and then heated to 80°C to about 120°C. The sodium 3-chloro-2-hydroxypropane-1 -sulfonate may be commercially supplied or prepared. According to one embodiment, the initial process flow evaluation may employ one 4000-gallon reactor and one 2000-gallon reactor (preparation of sodium 3-chloro-2-hydroxypropane-1 -sulfonate). According to one embodiment, any residual ethanol may be removed under vacuum at 80°C to about 120°C. The resultant castor amidopropyl sultaine (CAPS) may be diluted with water. The finished castor amidopropyl sultaine (CAPS) may be a thick syrup with a 20-30% wt / wt amber solution.

[0034] A method for preparing castor amidopropyl sultaine (CAPS) from castor oil is provided and is set forth in Figure 3.

[0035] According to one embodiment, the method includes the initial step of charging castor oil and N1 ,N 1 -dimethylpropane-1 ,3-diamine to a reaction vessel, followed by a catalytic amount of sodium methoxide to produce castor-DMAPA and glycerol. The reaction may be warmed at about 80°C to about 120°C. Methanol may be removed from the reaction, for example, via a Dean-Stark trap. Any excess castor-DMAPA may be removed under high vacuum at about 110°C to about 120°C to yield (R,Z)-N-(3-(dimethylamino)propyl)-12-hydroxyoctadec-9-enamide (castor-DMAPA)(see Step 1 of Figure 3).

[0036] According to one embodiment, the method includes the step of alkylating castor- DMAPA with sodium 3-chloro-2-hydroxypropane-1 -sulfonate (see Step 2 of Figure 3) in a EtOH / FhO mixture at about 80°C to about 120°C to afford the final amphoteric product, castor amidopropyl sultaine (CAPS). Any residual ethanol may be removed under vacuum at 80°C to about 120°C. The resultant castor amidopropyl sultaine (CAPS) may be diluted with water. The finished castor amidopropyl sultaine (CAPS) may be a thick syrup with a 20-30% wt / wt amber solution.

[0037] A method of preparing shea-based 3-(nonadecanoyloxy)propane-1 ,2-diyl dioleate (methyl oleate) is provided. The methyl oleate may serve as a starting material for preparing shea-based surfactants. According to one embodiment, the method of preparing methyl oleate includes the step of mixing shea oil and methanol. Such mixing may occur at room temperature. According to one embodiment, the method of preparing methyl oleate includes the step of adding sodium methanolate to the shea oil and methanol mixture to form a reaction mixture. According to one embodiment, the method of preparing methyl oleate includes the step of heating the reaction mixture for form an emulsion having a top phase and bottom phase.The step of heating may include warming the reaction mixture to about 50°C for about five hours. According to one embodiment, the method of preparing methyl oleate includes the step of concentrating the top phase to remove residual methanol and form solid shea-based methyl oleate. The step of concentrating may include heating to about 50°C.

[0038] A method of preparing shea-based 2-oleamidoethane-1 -sulfonate (oleoyl taurate or shea taurate) is provided. According to one embodiment, the method of preparing oleoyl taurate includes the step of heating a reaction mixture that includes 2-aminoethan-1 -sulfonate, methanol, shea-based methyl oleate, and sodium methanolate. The shea-based methyl oleate may be obtained from shea oil according to methods provided herein. According to one embodiment, the method of preparing oleoyl taurate includes the step of heating the reaction mixture to about 120°C for about six hours. According to one embodiment, the method of preparing oleoyl taurate includes the step of performing a first dilution of the reaction mixture with water. According to one embodiment, the method of preparing oleoyl taurate includes the step of adjusting the pH to about 8. The pH may be adjusted with any suitable acid such as hydrogen chloride. According to one embodiment, the method of preparing oleoyl taurate includes the step of performing a second dilution of the reaction mixture with water. According to one embodiment, the method of preparing oleoyl taurate includes the step of heating the reaction mixture to form oleoyl taurate. The step of heating may include warming the reaction mixture from about 65°C to about 95°C over about a four-hour period.Methods of Use and Performance

[0039] The surfactant compounds provided herein may be utilized as a surfactant in a variety of personal care compositions including, but not limited to, shampoos, conditioners, or body washes. According to another embodiment, the surfactant compounds provided herein may be utilized as a surfactant in facial cleansing soaps and masks. The personal care compositions provided herein may be formulated as liquids, solids, semi-solids, flakes, gels, aerosols, masks, or foams. Any of the surfactant compounds as provided herein may be utilized as a surfactant in their nonionic, cationic, anionic, or amphoteric forms. The surfactant compounds as provided herein may be utilized as primary or secondary surfactants as well as an adjunct in blending with other surfactants or typical components found in personal care compositions.

[0040] According to another embodiment, the surfactant compounds provided herein may be utilized in various environments including homecare, industrial, agriculture and pharmaceuticals. According to one embodiment, the surfactant compounds provided hereinmay be utilized as a surfactant in dish detergents, laundry detergents or fabric conditioners. According to one embodiment, the surfactant compounds provided herein may be utilized as a surfactant in bucket dilutable cleaning compositions. Such bucket dilutable cleaning compositions may include a detergent or other cleaning component, a surfactant compound as provided herein, and water or other carrier that is introduced by an end user prior to use.

[0041] According to one embodiment, the surfactant compounds provided herein demonstrate foam height, formation stability, odor, color, clarity, and solubility that compare favorably with or are superior to traditional personal care surfactants such as cocoyl amidopropyl sultaine or a traditional sulfate-containing surfactant. The surfactant compounds provided herein may provide an acceptable foam height for a time frame acceptable for the particular formulation.

[0042] According to one embodiment, the surfactant compounds provided herein exhibit a stable, clear amber solution with a mild odor that is suitable for use in personal care formulations. According to one embodiment, the surfactant compounds provided herein function through a wide pH range without deleterious effects.

[0043] According to one embodiment, the surfactant compounds provided herein may be combined to form a surfactant blend or premix. According to one embodiment, the surfactant compounds provided herein may be used in combination with sodium chloride for thickening personal care formulations. According to one embodiment, the surfactant compounds provided herein may be utilized as a co-surfactant with sulfate-containing surfactants such as sodium lauryl ether sulfate.

[0044] Although specific embodiments of the present invention are herein illustrated and described in detail, the invention is not limited thereto. The above detailed descriptions are provided as exemplary of the present invention and should not be construed as constituting any limitation of the invention. Modifications will be obvious to those skilled in the art, and all modifications that do not depart from the spirit of the invention are intended to be included with the scope of the appended claims.EXAMPLES

[0045] NMR spectra described in the Examples were acquired on a Varian Mercury 400 Plus NMR at 400 MHz for 1 H, 100 MHz for 13C, and chemical shifts were recorded in parts per million (ppm) relative to a tetramethylsilane (TMS) standard.EXAMPLE 1Synthesis of 2-hydroxy-3-((3-((R,Z)-12-hydroxyoctadec-9- enamido)propyl)dimethylammonio)propane-1 -sulfonate (Castor amidopropyl sultaine-CAPS)

[0046] A two-liter 4-necked flask was fitted with mechanical stirring, thermocouple, temperature controller with heating mantle and a Dean-Stark trap with condenser. The flask was charged with N1 ,N1 -dimethylpropane-1 ,3-diamine (DMAPA) (149 g, 183 mL, 1.15 Eq, 1.46 mol) and methyl (R,Z)-12-hydroxyoctadec-9-enoate (400 g, 433 mL, 99% Wt, 1 Eq, 1.27 mol) and stirred at ambient temperature for 10 minutes. To the resulting thick solution was added sodium methanolate (16.0 g, 16 mL, 30% Wt, 0.07 Eq, 88.7 mmol) in one portion. The resulting slurry was slowly warmed to 80°C. After methanol generation ceased, the system was sealed, stirred under high vacuum (20 mmHg), and slowly warmed to 1 10°C -120°C to remove excess amine. The reaction was stirred vigorously and held at 110-120 °C at 20 mmHg for six hours to completely remove the amine. The resulting product was a thick viscous opaque caramel syrup and used as is. The castor-DMAPA product was confirmed by 1 H NMR and 13C NMR (MeOH- d4).Synthesis of Sodium 3-chloro-2-hydroxypropane-1 -sulfonate

[0047] A one-liter 4N round bottom flask reaction vessel fit with overhead stirrer, thermocouple, syringe pump and reflux condenser was charged with sodium hydrogen sulfite (330 g, 236 mL, 40% Wt, 1 Eq, 1.27 mol) and water (200 mL) and heated to 50°C. Then, 2- (chloromethyl)oxirane (118 g, 99.6 mL, 1 Eq, 1 .27 mol) was added via syringe pump over 2.5 hrs. Upon complete addition, the reaction was warmed at 50°C for 4 hours. The heating was discontinued and the reaction allowed to cool to ambient temperature as it stirred overnight. Water (100 mL) was added to the suspension and warmed to 6°C to afford complete solution (45 %wt / wt product). The sodium 3-chloro-2-hydroxypropane-1 -sulfonate product was confirmed by 1 H NMR (DMSO-d6) of aqueous solution.Synthesis of 2-hydroxy-3-((3-((R,Z)-12-hydroxyoctadec-9-enamido)propyl)dimethylammonio)- propane-1 -sulfonate (Castor amidopropyl sultaine-CAPS)

[0048] A two-liter 4-neck round bottom flask fitted with overhead stirrer, reflux condenser / dean stark and thermocouple was charged with (R,Z)-N-(3-(dimethylamino)propyl)-12-hydroxyoctadec-9-enamide (486 g, 1 Eq, 1 .27 mol), ethanol (300 mL) and water (200 mL) and warmed to 50°C to afford efficacious stirring. To this reaction mixture was added sodium 3- chloro-2-hydroxypropane-1 -sulfonate (555 g, 45% Wt, 1 .00 Eq, 1 .27 mol) and the resulting reaction mixture warmed at 90°C for 6 hours.

[0049] To remove any residual EtOH or other volatile components, the reaction mixture was stirred vigorously as the pressure in the reaction vessel was slowly reduced from 700 torr to 30 torr as the reaction cooled to 35°C. Vacuum was discontinued and the reaction mixture was allowed to cool to ambient temperature as it stirred overnight.

[0050] A reaction mixture with the consistency of custard with a huge foam head was present. Additional Water (500 mL) was added and reaction stirred very slowly as it was warmed to 70°C. Stirring was intermittently increased to high RPM and returned to low RPM to incorporate foam head. After two hours, foam head was minimal on the surface of an amber solution. Yield was 2100 g, 31 .5% wt / wt product, 3.5% wt / wt NaCI. The castor amidopropyl sultaine (CAPS) product was confirmed by 1 H NMR and 13C NMR in MeOH-d4. The gravimetric density calculation was as follows: 10 mL = 10.5 g; d = 1 .05 g / mL.EXAMPLE 2Synthesis of (R,Z)-N-(3-(dimethylamino)propyl)-12-hydroxyoctadec-9-enamide (DMAPA)

[0051] A 500 mL 4-neck round bottom flask fitted with overhead stirrer, reflux condenser / dean stark and thermocouple was charged with AA Standard Castor Oil (propane- 1 ,2,3-triyl (9Z,9'Z,9"Z,12S,12'S,12"S)-tris(12-hydroxyoctadec-9-enoate)) (55 g, 1 Eq, 59 mmol) and Methanol (30 g) and N1 ,N1 -dimethylpropane-1 ,3-diamine (22 g, 27 mL, 3.6 Eq, 0.21 mol). Sodium methanolate (3.7 g, 3.8 mL, 30% Wt, 0.35 Eq, 21 mmol) was added to this stirred solution and the resulting reaction mixture incrementally warmed by 5°C from 70°C to 120°C until generation of methanol slowed markedly (~2 hours).

[0052] After methanol generation ceased, the system was sealed, stirred under high vacuum (20 mmHg), and slowly warmed to 110°C -120°C to remove excess amine. The reaction was stirred vigorously and held at 1 10-120 °C at 20 mmHg for six hours to completely remove the amine. The resulting product was a thick viscous caramel syrup and used as is. The castor-DMAPA product was confirmed by 1 H NMR and 13C NMR (MeOH-d4).Synthesis of 2-hydroxy-3-((3-((R,Z)-12-hydroxyoctadec-9-enamido)propyl)dimethylammonio)- propane-1 -sulfonate (Castor amidopropyl sultaine-CAPS)

[0053] A 500 mL 4-neck round bottom flask fitted with overhead stirrer, reflux condenser / dean stark trap and thermocouple was charged with (R,Z)-N-(3- (dimethylamino)propyl)-12-hydroxyoctadec-9-enamide (67 g, 1 Eq, 0.18 mol), ethanol (30 g) and water (60 g) and warmed to 50°C to afford efficacious stirring. A 60°C solution of sodium 3- chloro-2-hydroxypropane-1 -sulfonate (102 g, 34.2% Wt, 1.0 Eq, 0.18 mol) was added to the reaction mixture in one portion. The resulting reaction mixture warmed at 90°C for 6 hours. No more distillate was produced after 4 hours.

[0054] To remove any residual EtOH or other volatile components, the reaction mixture was stirred vigorously as the pressure in the reaction vessel was slowly reduced from 700 torr to 30 torr as the reaction cooled to 35°C. Vacuum was discontinued and the reaction mixture was allowed to cool to ambient temperature as it stirred overnight to afford a clear amber solution of castor amidopropyl sultaine (CAPS). Yield was 316.5 g; 28.8% wt / wt product; 3.3% wt / wt NaCI; 5.1 %wt / wt Glycerol. The gravimetric density calculation was as follows: 10 mL = 10.4 g; d = 1 .04 g / mL.EXAMPLE 3Synthesis of (R,Z)-2-((3-(12-hydroxyoctadec-9-enamido)propyl)dimethylammonio)acetate (Castor amidopropyl betaine (CAPB))

[0055] A 500 mL 4-neck round bottom flask fitted with overhead stirrer, reflux condenser / dean stark trap and thermocouple was charged with (R,Z)-N-(3- (dimethylamino)propyl)-12-hydroxyoctadec-9-enamide (25 g, 1 Eq, 65.3 mmol), Ethanol (25 g) and Water (75 g) and stirred at ambient temperature. To this reaction mixture was added sodium 2-chloroacetate (7.76 g, 1.02 eq, 66.6 mmol) in one portion. The resulting reaction mixture was stirred at 80°C for 6 hours.

[0056] The reaction mixture was warmed to 85°C until no more distillate was produced.The reaction mixture was then heated to 110°C to reduce the volume of water to afford a clear amber syrup. 1 H NMR (D2O) and 13C NMR (D2O) confirmed product.

[0057] The final mass of product aqueous solution was 118 g; 24.5 % wt / wt product ; 3.2 % wt / wt NaCI.EXAMPLE 4Synthesis of (R,Z)-2-((2-(12-hydroxyoctadec-9-enamido)ethyl)dimethylammonio)acetate (Castor amidoethyl betaine (CAEB))Synthesis of (R,Z)-N-(2-(dimethylamino)ethyl)-12-hydroxyoctadec-9-enamide (Castor amidoethyl amine-CAEA) - Preparation 1

[0058] A 250 mL 4-neck round bottom flask fitted with overhead stirrer, reflux condenser / dean stark and thermocouple was charged with N1 ,N1-dimethylethane-1 ,2-diamine (17 g, 21 mL, 97% Wt, 1.2 Eq, 0.19 mol) and methyl (R,Z)-12-hydroxyoctadec-9-enoate (50 g, 54 mL, 99% Wt, 1 Eq, 0.16 mol) and stirred at ambient temperature for 10 minutes.

[0059] Sodium methanolate (3.0 g, 3.1 mL, 30% Wt, 0.11 Eq, 17 mmol) was added and the reaction slowly warmed to 120°C until the formation of methanol ceased. After which time, the pressure of the reaction mixture was slowly lowered to 15 torr and stirred @ 120°C for 4 hours to remove residual starting amine.

[0060] The reaction mixture was allowed to cool to ambient temperature to provide a thick caramel colored semi-solid. 1 H NMR in MeOH-d4 confirmed product with no starting amine present and was suitable purity to use in next step with quantitative yield.Synthesis of (R,Z)-2-((2-(12-hydroxyoctadec-9-enamido)ethyl)dimethylammonio)acetate (Castor amidoethyl betaine (CAEB))

[0061] A 500 mL 4-neck round bottom flask fitted with overhead stirrer, reflux condenser / dean stark and thermocouple was charged with (R,Z)-N-(2-(dimethylamino)ethyl)-12- hydroxyoctadec-9-enamide (60.0 g, 1 Eq, 163 mmol), Ethanol (50 mL, 40 g) and Water (150 mL, 150 g) and stirred at ambient temperature for 10 minutes.

[0062] Sodium 2-chloroacetate (19.3 g, 1 .02 Eq, 166 mmol) was added in one portion and the reaction warmed at 80°C for 6 hours. The reaction mixture was then slowly warmed to 110°C to remove ethanol and concentrate the solution. The reaction was allowed to cool to ambient temperature to afford a thick amber syrup. 1 H NMR and 13 C NMR in MeOH-d4 confirmed product.

[0063] The final mass of aqueous product was 206.4 g; Product = 33.6% wt / wt; NaCI = 4.5% wt / wt.EXAMPLE 5Synthesis of 2-hydroxy-3-((2-((R,Z)-12-hydroxyoctadec-9- enamido)ethyl)dimethylammonio)propane-1 -sulfonate (Castor amidoethyl sultaine (CAES)

[0064] A 500 mL 4-neck round bottom flask fitted with overhead stirrer, reflux condenser / dean stark and thermocouple was charged with (R,Z)-N-(2-(dimethylamino)ethyl)-12- hydroxyoctadec-9-enamide [Example 4, prep 1] (55 g, 1 Eq, 0.15 mol) ethanol (50 mL) and Water (20 mL). The resulting cloudy solution was stirred at ambient temperature as sodium 3- chloro-2-hydroxypropane-1 -sulfonate [Example 1 , prep 1] (69 g, 42.6% Wt, 1 Eq, 0.15 mol) was added in one portion. The reaction mixture was warmed at 90°C for 6 hours.

[0065] The reaction mixture was warmed to 95°C until no more distillate was produced.The reaction mixture was then heated to 110°C to reduce the volume of water to afford a clear amber solution. 1 H NMR (D2O) and 13C NMR (D2O) confirmed product. The final mass of product aqueous solution was 225 g; 33.7 % wt / wt product ; 3.9% wt / wt NaCLEXAMPLE 6Synthesis of (R,Z)-3-(12-hydroxyoctadec-9-enamido)-N,N,N-trimethylpropan-1 -aminium (Castor amidopropyl quat)

[0066] A 250 mL 4-neck round bottom flask fitted with overhead stirrer, condenser, addition funnel and thermocouple, under a N2 atmosphere was charged with (R,Z)-N-(3- (dimethylamino)propyl)-12-hydroxyoctadec-9-enamide (57 g, 1 Eq, 0.15 mol) and stirred at 50°C as dimethyl sulfate (19 g, 14 mL, 1 Eq, 0.15 mol) was added dropwise. Upon complete addition the reaction was stirred at 60°C for 4 hours.

[0067] The reaction was quenched by dropwise addition of 2-Propanol (15 mL, 12 g) @60°C. Upon complete addition, the reaction was warmed at 80°C and I PA was removed under high vacuum. The product was transferred warm to a bottle. The yield was 66.4 g.EXAMPLE 7Synthesis of (R,Z)-(12-hydroxyoctadec-9-enoyl)glycine (Castor glycinate)

[0068] A 500 mL 4N round bottom flask fitted with overhead stirrer, condenser with Dean- Stark trap and thermocouple, was charged with glycine (13 g, 1 .05 eq, 0.17 mol) and 30 % sodium methanolate (33 g, 0.18 mol) and stirred at ambient temperature for 10 minutes to preform sodium glycinate. Methyl (R,Z)-12-hydroxyoctadec-9-enoate (50 g, 54 mL, 1 Eq, 0.16 mol) was added and the reaction was warmed at 80°C for four hours with removal of MeOH viaDean-Stark trap. The temperature was increased to 100°C and stirred for 30 minutes to ensure reaction had run to completion and all MeOH was removed. The reaction mixture was allowed to cool to 50°C and diluted with water (200 mL) to afford an amber solution. Contents were transferred to 1000 mL 4N round bottom flask, fit with overhead stirrer and thermocouple. Tetrahydrofuran (THF)(200 mL, 175 g) was added to the reaction vessel, and stirred until the solution became homogeneous. The pH of the solution was adjusted to pH = 3 with 5N HCI, stirred for 10 minute and transferred to a separatory funnel. The aqueous layer was removed and the organics washed with an additional volume of water. The organics were concentrated to dryness on a rotary evaporator and dried under high vacuum at 60°C overnight to afford the product as a beige solid. The yield was 43.6 g, 77 %.EXAMPLE 8Synthesis of ((R,Z)-12-hydroxyoctadec-9-enoyl)-L-glutamate (Castor glutamate)

[0069] A 500 mL 4-neck round bottom flask fitted with overhead stirrer, reflux condenser / dean stark and thermocouple was charged with sodium (S)-2-amino-4- carboxybutanoate (27 g, 1 Eq, 0.16 mol), Methanol (24 g, 30 mL) and methyl (R,Z)-12- hydroxyoctadec-9-enoate (50 g, 54 mL, 99% Wt, 1 Eq, 0.16 mol) and stirred at ambient temperature for 10 minutes. Sodium methanolate (34 g, 35 mL, 30% Wt, 1.2 Eq, 0.19 mol) was added and the reaction warmed at 90°C with removal of methanol via Dean-Stark trap for 2 hours. The reaction mixture then heated at 80°C under vacuum for 4 hours and then transferred to sample bottle. Upon cooling to ambient temperature, the reaction mixture solidified to thick waxy solid, light caramel in color. The pH was 10 and the yield was 73.8 g, 99 %.EXAMPLE 9Synthesis of (R,Z)-N-(12-hydroxyoctadec-9-enoyl)-N-methylglycinate (Castor Sarcosinate)

[0070] A flask was charged with methylglycine (Sarcosine) (15 g, 98% Wt, 1.05 Eq, 0.17 mol) and sodium methanolate (33 g, 34 mL, 30% Wt, 1.15 Eq, 0.18 mol) and stirred at ambient temperature for 10 minute to preform sodium sarcosinate. Methanol (30 mL, 24 g) and methyl (R,Z)-12-hydroxyoctadec-9-enoate (50 g, 54 mL, 1 Eq, 0.16 mol) were added and the reaction stirred at 75°C for four hours to remove methanol via Dean-Stark trap. The reaction was then warmed to 85°C under full vacuum (15 torr) for 3 hours to afford the desired product. The yield was 60 g, 96%.EXAMPLE 10Synthesis of ((R,Z)-12-hydroxyoctadec-9-enoyl)-L-phenylalaninate (Castor phenylalaninate)

[0071] A 500 mL 4-neck round bottom flask fitted with overhead stirrer, reflux condenser / dean stark and thermocouple was charged with L-phenylalanine (27 g, 1.05 Eq, 0.17 mol), Methanol (40 g, 50 mL) and methyl (R,Z)-12-hydroxyoctadec-9-enoate (50 g, 54 mL, 99% Wt, 1 Eq, 0.16 mol) and stirred at ambient temperature for 10 minutes. Sodium methanolate (64 g, 66 mL, 30% Wt, 2.25 Eq, 0.36 mol) was added and the reaction warmed at 75°C for 4 hours to remove methanol via Dean-Stark trap. The reaction was warmed to 85°C and stirred under high vacuum for 2 hours to afford the desired product as a solid upon cooling. The yield was 69.1 g, 93%.EXAMPLE 11Synthesis of ((R,Z)-12-hydroxyoctadec-9-enoyl)-L-prolinate (Castor prolinate)

[0072] A flask was charged with L-proline (18 g, 1 Eq, 0.16 mol) , Methanol (30 g, 50 mL) and sodium methanolate (36 g, 37 mL, 30% Wt, 1 .25 Eq, 0.20 mol) and stirred at ambient temperature for 10 minutes. Methyl (R,Z)-12-hydroxyoctadec-9-enoate (50 g, 54 mL, 99% Wt, 1 Eq, 0.16 mol) was added and the reaction warmed to reflux 75°C for 4 hours to remove methanol via Dean-Stark trap, and then placed reaction under high vacuum and stirred vigorously for two hours. The product solidified upon cooling. 100 mL water was added and stirred at 60°C until the solution was homogenous. The total weight of solution was 193.5 g. The final solution was 34.1 %wt / wt product.EXAMPLE 12Synthesis of (R,Z)-2-((12-hydroxyoctadec-9-enoyl)oxy)ethane-1 -sulfonate (Castor isethionate)

[0073] A 500 mL 4-neck round bottom flask fitted with overhead stirrer, reflux condenser / dean stark and thermocouple flask was charged with sodium 2-hydroxyethane-1 - sulfonate (24 g, 98% Wt, 1.02 Eq, 0.16 mol) , Methanol (24 g, 30 mL) and methyl (R,Z)-12- hydroxyoctadec-9-enoate (50 g, 54 mL, 99% Wt, 1 Eq, 0.16 mol) and stirred at ambient temperature for 10 minutes. Sodium methanolate (29 g, 29 mL, 30% Wt, 1.0 Eq, 0.16 mol) was added and the reaction warmed to 75°C for 4 hours with methanol removal via Dean-Stark trap.The reaction mixture then heated at 75°C under vacuum for 4 hours to afford a thick waxy solid, light caramel in color, slightly tacky but well behaved. The solids were triturated with methyl ethyl ketone (500 mL) and collected via vacuum filtration and dried on a rotary evaporator to afford the desired product as a tan solid. The yield was 47.7 g, 70%.EXAMPLE 13Synthesis of (R,Z)-2-(12-hydroxyoctadec-9-enamido)ethane-1 -sulfonate (Castor taurate)

[0074] A flask was charged with sodium 2-aminoethane-1 -sulfonate (24 g, 1 Eq, 0.16 mol), Methanol (125 g), methyl (R,Z)-12-hydroxyoctadec-9-enoate (50 g, 1 Eq, 0.16 mol) and sodium methanolate (23 g, 24 mL, 30% Wt, 0.8 Eq, 0.13 mol). The vessel was sealed and heated at 120°C for 16 hours and then diluted with water (100 g) and adjusted to pH = 8 with 5N hydrogen chloride. The contents were transferred to a 2L 4N round bottom flask fitted with overhead stirrer, thermocouple, and Dean-Stark trap + condenser and diluted with additional 300 g of water to afford an amber solution. The reaction mixture was reduced by heating at 90-95°C for 2 hours. When cooled, the resulting reaction mixture was a thick amber syrup. The total mass was 309.4 grams, and the product was 22.0 % wt / wt.EXAMPLE 14Synthesis of 2-(dimethyl(3-oleamidopropyl)ammonio)acetate (oleoyl amidopropyl betaine - shea based)N-(3-(dimethylamino)propyl)oleamide (oleoyl DMAPA)

[0075] A 500 mL 4-neck round bottom flask fitted with an overhead stirrer, reflux condenser / dean stark and thermocouple was charged with N1 ,N1-dimethylpropane-1 ,3-diamine (20 g, 1.2 Eq, 0.19 mol), methanol (30 g) and methyl oleate (48 g, 1 Eq, 0.16 mol) and stirred at ambient temperature for 10 minutes. Sodium methanolate (2.0 g, 30% Wt, 0.07 Eq, 11 mmol) was added and the reaction was slowly warmed to 100°C until generation of MeOH ceased (~2 hours). The reaction mixture was heated to 110°C for 2 hours under vacuum (15 mmHg).Upon cooling to ambient temperature, the reaction mixture became a thick opaque viscous caramel syrup. 58 g, 98%2-(dimethyl(3-oleamidopropyl)ammonio)acetate (oleoyl amidopropyl betaine)

[0076] A 500 mL 4-neck RBF fitted with an overhead stirrer, reflux condenser / dean stark and thermocouple was charged with N-(3-(dimethylamino)propyl)oleamide (58 g, 1 Eq, 0.16 mol), Ethanol (40 g) and water (150 mL, 150 g) and stirred at ambient temperature for 10 minutes. Sodium 2-chloroacetate (19 g, 1.02 Eq, 0.16 mol) was added in one portion and the reaction warmed at 85°C for 6 hours, then warmed at 95°C until no more distillate was produced. Heating was discontinued and pressure then reduced to 100 mmHg for 2 hours. Additional water was added to ease transfer. The total mass was 275 g, 24.4 wt% product.EXAMPLE 15Synthesis of 3-(dimethyl(3-oleamidopropyl)ammonio)-2-hydroxypropane-1 -sulfonate (oleoyl amidopropyl sultaine)

[0077] A 500 mL 4-neck round bottom flask fitted with overhead stirrer, reflux condenser / dean stark and thermocouple flask was charged with N-(3- (dimethylamino)propyl)oleamide (59 g, 1 Eq, 0.16 mol) Ethanol (30 g) and water (70 g) and stirred at ambient temperature for 10 minutes. Sodium 3-chloro-2-hydroxypropane-1 -sulfonate (74 g, 42.6% Wt, 1 Eq, 0.16 mol) (see Example 1), was added in one portion and the reaction warmed at 85°C until no more distillate was produced (~6 hours). The pressure was slowly decreased from 700 to 15 mmHg and held for 2 hours . Water (70 g) was added to the reaction mixture under atmospheric pressure and transferred to 16 oz wide mouth jar. The total mass was 233.5 g, 34.7 %wt product.EXAMPLE 16Synthesis of 3-(dimethyl(3-stearamidopropyl)ammonio)-2-hydroxypropane-1 -sulfonate (stearyl amidopropyl sultaine)N-(3-(dimethylamino)propyl)stearamide (stearyl DMAPA)

[0078] A 500 mL 4-neck round bottom flask fitted with overhead stirrer, reflux condenser / dean stark and thermocouple was charged with methyl stearate (50 g, 1 Eq, 0.17 mol) and methanol (85 g) and stirred at ambient temperature for 10 min to afford a free moving suspension. N1 ,N1 -dimethylpropane-1 ,3-diamine (21 g, 1.2 Eq, 0.20 mol) then sodium methanolate (30 g, 30% Wt, 1 Eq, 0.17 mol) were sequentially added and the resulting reaction mixture slowly warmed to 80°C. The mixture was heated at atmospheric pressure untilgeneration of MeOH slowed markedly (~2 hours). Heat was increased to 120 °C until generation of MeOH ceased. The pressure was slowly decreased from 700 mmHg to 15 mmHg held under full vacuum (~15 mmHg) for 4 hours. Upon cooling to ambient temperature, the reaction mixture became a thick opaque viscous caramel syrup 62 g; 100 %.3-(dimethyl(3-stearamidopropyl)ammonio)-2-hydroxypropane-1 -sulfonate (stearyl amidopropyl sultaine)

[0079] A 500 mL 4-neck round bottom flask fitted with overhead stirrer, reflux condenser / dean stark and thermocouple flask was charged with N-(3- (dimethylamino)propyl)stearamide (62 g, 1 Eq, 0.17 mol), Methanol (50 g) and Water (50 g) and warmed to 45°C to afford efficient stirring. The suspension was stirred at 45°C for 10 minutes. Sodium 3-chloro-2-hydroxypropane-1 -sulfonate (97 g, 34.2% Wt, 1 Eq, 0.17 mol) was added in one portion. The resulting reaction mixture suspension was warmed at 85°C until no more distillate was produced (~6 hours). Water (50 g) was added to the reaction mixture warmed at 85°C to afford a thick suspension. Reaction mixture was heated to 85°C and pressure was slowly decreased from 700 to 250 mmHg. The reaction was held at 250 mmHg for 2 hours.Water (50 g) was added to assist in transfer to 32 oz wide mouth jar. The mass of contents was 477.2 grams; 17.8 %wt / wt product.EXAMPLE 17Synthesis of 2-oleamidoethane-1 -sulfonate (oleoyl taurate)Preparation from sodium 2-aminoethane-1 -sulfonate (sodium taurate)

[0080] A 2L 4N-round bottom flask with overhead stirrer and N2 inlet flask was charged with 2-aminoethane-1 -sulfonic acid (195 g, 1 Eq, 1.56 mol) and Methanol (400 g). The resulting suspension was vigorously stirred at ambient temperature as sodium methanolate (286 g, 0.30 L, 30% Wt, 1.02 Eq, 1.59 mol) was poured portion wise into the reaction vessel.

[0081] Upon complete addition, the suspension was blanketed with N2 and stirred at ambient temperature for 2 hours. Additional Methanol (450 g) was added to afford efficacious stirring. Solids were collected via vacuum filtration. Filtrate was concentrated to dryness on the rotovap. All solids combined and dried under high vacuum at 60°C overnight to yield 213 g, 93%.Preparation from methyl oleate (palm based)

[0082] A flask was charged with sodium 2-aminoethane-1 -sulfonate (25 g, 1 Eq, 0.17 mol), methanol (120 g), methyl oleate-96% (50 g, 1 Eq, 0.17 mol) and sodium methanolate (24 g, 25 mL, 30% Wt, 0.8 Eq, 0.13 mol). The vessel was sealed and heated at 120 °C for 16 hrs. The reaction mixture was a cream-colored suspension. Water (100 g) was added to parr reactor and adjusted to a pH of 8 with hydrogen chloride (5.5 g, 30 mL, 5 molar, 0.9 Eq, 0.15 mol).

[0083] The contents were transferred to a 2L 4N-round bottom flask fit with thermocouple, overhead stirrer, dean-stark trap with condenser and air inlet. The reaction mixture was diluted with additional Water (350 g) to afford an amber solution. A positive sweep of air was initiated and the temperature slowly raised from 65-97 °C (avoiding foaming into Dean-Stark trap) over a four-hour period to remove methanol.

[0084] The product was a thick cream colored, opaque gel. The product was transferred to 16 oz jar. The total mass was 421 grams: 16.4 %wt / wt.Preparation of methyl oleate from Shea Oil (shea-based)

[0085] Under a blanket of N2, a flask was charged with shea oil (750 g, 1 Eq, 832 mmol) and methanol (267 g, 337 mL, 10 Eq, 8.32 mol) and stirred at room temperature. Sodium methanolate (59.9 g, 30% Wt, 0.4 Eq, 333 mmol) was added in one portion and the resulting reaction mixture warmed at 50°C for five hours and the entire contents of the reaction was transferred to a 2L separatory funnel. A clear split was present. The lower phase was a clear orange, and the upper phase was a slightly hazy pale yellow. The bottom phase was removed, and the top phase was transferred to a 2 L round bottom flask and concentrated on a rotovap at 50°C to remove any residual methanol.

[0086] The product was allowed to cool to ambient temperature as it sat overnight. Significant solids were precipitated from solution. Solids were removed via vacuum filtration to yield a straw yellow syrup. The yield was 727 g; 96% mass recovery; 80% (GC) oleate content.Purification of methyl oleate

[0087] The purity of the methyl oleate was enhanced to >96% by a two-step low temperature crystallization from acetone.

[0088] Step 1 : 10:1 acetone:oleate chilled to -40 °C. Solids were removed by vacuum filtration, (solids contain palmitate and stearate esters). The filtrate was concentrated and taken to next step.

[0089] Step 2: 15:1 acetone: oleate chilled to -70 °C. Solids were removed via vacuum filtration and washed with additional portion of -70 °C acetone. Solids containing purified methyl oleate were transferred to jar. The oleate content was 96% (GC).Preparation of oleoyl taurate from shea-based methyl oleate

[0090] A flask was charged with sodium 2-aminoethane-1 -sulfonate (25 g, 1 Eq, 0.17 mol), methanol (120 g), Shea based methyl oleate (50 g, 1 Eq, 0.17 mol) and sodium methanolate (24 g, 25 mL, 30% Wt, 0.8 Eq, 0.13 mol). The vessel was sealed and heated at 120°C for 16 hours.

[0091] The reaction mixture was a cream-colored suspension. Water (100 g) was added to parr reactor and adjusted to pH = 8 with hydrogen chloride (6.0 g, 33 mL, 5 molar, 0.97 Eq, 0.16 mol).

[0092] The contents were transferred to a 2L 4N-round bottom flask fit with thermocouple, overhead stirrer, dean-stark trap with condenser and air inlet. The reaction mixture was diluted with additional Water (350 grams) to afford an amber solution. A positive sweep of air was initiated and the temperature slowly raised from 65-95°C (foaming into Dean-Stark trap was avoided) over a four-hour period to remove methanol. The product was a thick amber gel which became a white paste upon cooling to ambient temperature. The total mass was 337 grams; 20 %wt / wt.

Claims

CLAIMSWe claim:1 . A castor-based surfactant compound of Formula (I):Formula (I) wherein: n is 0, 1 , 2, 3 or 4; x is 3, 4, 5 or 6;L is a Ci-C8linker group that is either fully saturated or has one or more degrees of unsaturation;Ri is H, OH, or CH3;R2 is C1-C12 alkyl;R3is NH, NCH3, O, or R3is N and together with R4forms an optionally substituted heterocyclic2. The surfactant compound of claim 1 , wherein R2 is Ce-alkyl.

3. The surfactant compound of claims 1 or 2, wherein the optionally substituted heterocyclic ring i4. A castor-based surfactant compound selected from the group consisting of: (R,Z)-2-((3-(12-hydroxyoctadec-9-enamido)propyl)dimethylammonio)acetate (castor amidopropyl betaine (CAPB));2-hydroxy-3-((3-((R,Z)-12-hydroxyoctadec-9-enamido)propyl)dimethylammonio)propane-1 - sulfonate (castor amidopropyl sultaine (CAPS));(R,Z)-2-((2-(12-hydroxyoctadec-9-enamido)ethyl)dimethylammonio)acetate (castor amidoethyl betaine (CAEB));(2-hydroxy-3-((2-((R,Z)-12-hydroxyoctadec-9-enamido)ethyl)dimethylammonio)propane-1 - sulfonate (castor amidoethyl sultaine (CAES));(R,Z)-3-(12-hydroxyoctadec-9-enamido)-N,N,N-trimethylpropan-1-aminium (castor amidopropyl quat);(R,Z)-12-hydroxyoctadec-9-enoyl)-L-prolinate;(R,Z)-12-hydroxyoctadec-9-enoyl)-L-phenylalaninate;(R,Z)-(12-hydroxyoctadec-9-enoyl)glycine;(R,Z)-N-(12-hydroxyoctadec-9-enoyl)-N-methylglycinate;(R,Z)-12-hydroxyoctadec-9-enoyl)-L-glutamate;(R,Z)-2-(12-hydroxyoctadec-9-enamido)eth an e-1 -sulfonate;(R,Z)-2-((12-hydroxyoctadec-9-enoyl)oxy)ethane-1 -sulfonate;2-((9Z,12Z)-octadeca-9,12-dienamido)ethane-1 -sulfonate; and methyl (9Z,12Z)-octadeca-9,12-dienoate (methyl linoleate).

5. A shea-based surfactant compound of Formula (II)Formula (II) wherein: n is 0, 1 , 2, 3 or 4;Rs is C1-C14 alkyl;6. A shea-based surfactant compound selected from the group consisting of:2-(dimethyl(3-oleamidopropyl)ammonio)acetate (oleoyl amidopropyl betaine);3-(dimethyl(3-oleamidopropyl)ammonio)-2-hydroxypropane-1 -sulfonate (oleoyl amidopropyl sultaine); and2-oleamidoethane-1 -sulfonate (oleoyl taurate).

7. A personal care composition comprising: a surfactant compound of any one of claims 1-6; and one or more acceptable carriers, wherein the personal care composition is formulated as a body wash, hair conditioner, or shampoo.

8. A cleaning composition comprising: a surfactant compound of any one of claims 1-6; and one or more acceptable carriers, wherein the cleaning composition is formulated as a bucket dilutable formulation.

9. A method of preparing castor amidopropyl sultaine (CAPS), the method comprising the steps of: condensing N,N’-dimethylaminopropylamine (DMAPA) with castor-based methyl ricinoleate in the presence of a catalytic amount of sodium methoxide and, optionally, methanol to form castor-DMAPA; adding epichlorohydrin over about 2.5 hours to a 50°C solution of about 40% sodium bisulfite to produce sodium 3-chloro-2-hydroxypropane-1 -sulfonate; andalkylating castor-DMPA with sodium 3-chloro-2-hydroxypropane-1 -sulfonate in aEtOH / H2O mixture at about 80°C to about 90°C to produce castor amidopropyl sultaine (CAPS).

10. The compound, castor amidopropyl sultaine (CAPS), produced according to the steps of claim 9.

11. A method of preparing castor amidopropyl sultaine (CAPS), the method comprising the steps of: condensing N,N’-dimethylaminopropylamine (DMAPA) with castor oil in the presence of a catalytic amount of sodium methoxide and, optionally, methanol to form castor-DMAPA and glycerol; and alkylating castor-DMPA with sodium 3-chloro-2-hydroxypropane-1 -sulfonate in a EtOH / H2O mixture at about 80°C to about 90°C to produce castor amidopropyl sultaine (CAPS).

12. The compound, castor amidopropyl sultaine (CAPS), produced according to the steps of claim 11 .

13. A method of preparing shea-based 3-(nonadecanoyloxy)propane-1 ,2-diyl dioleate (methyl oleate), the method comprising the steps of: mixing shea oil and methanol; adding sodium methanolate to the shea oil and methanol mixture to form a reaction mixture; heating the reaction mixture for form an emulsion having a top phase and bottom phase; and concentrating the top phase to remove residual methanol and form solid shea-based methyl oleate.

14. The compound, 3-(nonadecanoyloxy)propane-1 ,2-diyl dioleate (methyl oleate), produced according to the steps of claim 13.

15. A method of preparing shea-based 2-oleamidoethane-1 -sulfonate (oleoyl taurate), the method comprising the steps of: heating a reaction mixture comprising 2-aminoethan-1 -sulfonate, methanol, shea-based methyl oleate, and sodium methanolate;performing a first dilution of the reaction mixture with water; adjusting the pH to about 8; performing a second dilution of the reaction mixture with water; and heating the reaction mixture to form oleoyl taurate.

16. The compound, 2-oleamidoethane-1 -sulfonate (oleoyl taurate), produced according to the steps of claim 15.