Amphoteric ester sulfonate

Abstract

The present invention relates to amphoteric ester sulfonates. Various amphoteric ester sulfonates of formula 1 are disclosed herein, including 3-(N,N-dimethyl-cocoylpropylammonio-1-yl)-2-hydroxypropanesulfonate. These amphoteric ester sulfonates can be advantageously prepared by a two-step chemoenzymatic method with high yield and purity and have excellent surfactant properties. R is C3-C 23 Hydrocarbon; R 1 is a C1-C8 hydrocarbon group; R 2 and R 3 Each is independently selected from C1-C6 alkyl, C1-C6 diene, C1-C6 triene and C3-C8 cycloalkyl; wherein R 1 , R 2 and R 3 At least two of them can be combined with N + connected to form a heterocyclic ring; and R 4 It is a C1-C8 hydrocarbon group.

Description

[0001] This application is a divisional application, the application date of the parent application is October 13, 2015, the application number is 201580056526.4, and the name of the invention is “ampholytic ester sulfonate”. Technical Field

[0002] The present invention relates generally to amphoteric ester sulfonates. More specifically, the present invention relates to quaternary ammonium ester sulfonates, compositions of such compounds, uses of such compounds, and methods for making them. The invention disclosed or claimed herein was made pursuant to a Joint Research Agreement between Eastman Chemical Company and Johnson & Johnson Consumer & Personal Products Worldwide, a division of Johnson & Johnson Consumer Companies Inc. Background Art

[0003] There is an increasing need in industry and society for safer and more environmentally friendly ingredients and methods for preparing those ingredients. In particular, it is highly desirable to provide methods that reduce or minimize the use of irritating or allergenic starting materials, use biocompatible agents, and optimally use starting materials obtained from natural sources or that are "nature equivalents". This is an urgent need for consumer-facing industries such as personal care and home care.

[0004] One type of material that may approach a "greener" approach is surfactants. In particular, there is a need for new amphoteric surfactants that avoid the use of irritating or allergenic starting materials and are prepared in a more environmentally friendly manner.

[0005] Amphoteric (or zwitterionic) surfactants are used throughout the personal and home care industry. They are classified as specialized co-surfactants that complement the performance of primary surfactants. These co-surfactants also improve the mildness of the formulation by reducing the irritation associated with pure ionic surfactants.

[0006] The most common zwitterionic sulfonate surfactants are amide-amine based materials prepared by a multistep process from coconut or palm kernel oil and N,N-dimethylamino-3-propylamine (DMAPA). Several patents (US 3,280,179; US 4,259,191) and publications (Parris et al. J. Am. Oil Chem. Soc., Vol. 54, pp. 294-296 (1977)) details common preparation methods for these types of materials. These methods generally involve amidation of fatty acids with DMAPA at elevated temperatures (150-175°C). The intermediate fatty amino-amide is then reacted with a hydrophilic substance such as propane sultone or sodium 3-chloro-2-hydroxypropane sulfonate to produce the final zwitterionic surfactant.

[0007] These methods have some drawbacks. For example, typical amidation methods require high temperatures for conversion and distillation to remove unreacted starting materials. These high reaction temperatures may produce by-products and impart color to the product, requiring additional steps to remove the by-products and color.

[0008] In addition, DMAPA is a known sensitizer, as is the corresponding amido-amine. Both are present in trace amounts in the final formulation.

[0009] Therefore, there is a need for zwitterionic / zwitterionic surfactants that can be prepared under milder conditions and without the use of DMAPA or DMAPA amide.

[0010] The present invention addresses this and other needs as will become apparent from the following description and appended claims. Summary of the invention

[0011] The invention is set out in the appended claims.

[0012] Briefly, in one aspect, the present invention provides compounds having Formula 1:

[0013]

[0014] in

[0015] R is C 3 -C 23 Hydrocarbon;

[0016] R 1 C 1 -C 8 Hydrocarbon;

[0017] R 2 and R 3 Each independently selected from C 1 -C 6 Alkyl, C 1 -C 6 Alkenyl, C 1 -C 6 Dienyl, C 1 -C 6 Triene and C 3 -C 8 Cycloalkyl;

[0018] Where R 1 , R 2 and R 3 At least two of them can be combined with N + connected to form a heterocyclic ring; and

[0019] R 4 C 1 -C 8 Hydrocarbon.

[0020] In another aspect, the present invention provides a mixture comprising at least two compounds having Formula 1. The at least two compounds have at least one different R substituent.

[0021] In another aspect, the present invention provides a method for preparing a compound of formula 1. The method comprises: (a) contacting an acid or ester of formula 2 with a dialkylamino alcohol of formula 3 in the presence of an enzyme under conditions effective to form an intermediate of formula 4:

[0022]

[0023]

[0024] Among them, R 1 , R 2 and R 3 As defined above in Formula 1, R 7 is hydrogen or C 1 -C 6 Alkyl; and

[0025] (b) contacting the intermediate of formula 4 with a sulfonate alkylating agent under conditions effective to form a compound of formula 1.

[0026] In another aspect, the present invention provides a method for preparing a mixture comprising at least two compounds having Formula 1. The method comprises:

[0027] (a) contacting a mixture comprising at least two acids or esters of Formula 2 with a dialkylamino-alcohol of Formula 3 in the presence of an enzyme under conditions effective to form at least two intermediates of Formula 4:

[0028]

[0029]

[0030] in

[0031] R, R 1 , R 2 and R 3 As defined above in Formula 1,

[0032] R 7 is hydrogen or C1 -C 6 alkyl,

[0033] The at least two acids or esters of Formula 2 have different R substituents, and

[0034] The at least two intermediates of Formula 4 have different R substituents; and

[0035] (b) contacting the intermediate of formula 4 with a sulfonate alkylating agent under conditions effective to form a mixture of at least two compounds of formula 1. DETAILED DESCRIPTION

[0036] In one aspect, the present invention provides a series of amphoteric ester sulfonate compounds having Formula 1:

[0037]

[0038] in

[0039] R is C 3 -C 23 Hydrocarbon;

[0040] R 1 C 1 -C 8 Hydrocarbon;

[0041] R 2 and R 3 Each independently selected from C 1 -C 6 Alkyl, C 1 -C 6 Alkenyl, C 1 -C 6 Dienyl, C 1 -C 6 Triene and C 3 -C 8 Cycloalkyl;

[0042] Where R 1 , R 2 and R 3 At least two of them can be combined with N + connected to form a heterocyclic ring; and

[0043] R 4 C 1 -C 8 Hydrocarbon.

[0044] As used herein, the term "hydrocarbyl" refers to a monovalent or divalent hydrocarbon radical, depending on the context. The term includes traditional hydrocarbon radicals such as alkyl, alkene, alkyne, aryl, and cycloalkyl, as well as hydrocarbyl radicals such as alkylene, alkenylene, alkynylene, arylene, and cycloalkylene.

[0045] The hydrocarbon group of R can be substituted or unsubstituted; branched or straight chain; and saturated, monounsaturated, or polyunsaturated. The hydrocarbon group of R can also be substituted or unsubstituted C 3 -C 8 Cycloalkyl.

[0046] In a preferred embodiment, R is selected from substituted or unsubstituted, branched or linear, saturated C 5 -C 19 Alkyl; substituted or unsubstituted, branched or straight chain C 5 -C 17 Alkenyl; substituted or unsubstituted, branched or straight chain C 5 -C 17 Dienyl; and substituted or unsubstituted C 3 -C 8 Cycloalkyl.

[0047] The hydrocarbon group of R may be substituted by one to five substituents selected from the following: 1 -C 6 Alkoxy, C 1 -C 6 Carboxyl, C 1 -C 15 Aminocarbonyl, C 1 -C 15 Amide, cyano, C 2 -C 6 Alkoxycarbonyl, C 2 -C 6 Alkanoyloxy, hydroxy, aryl, heteroaryl, thioether, C 2 -C 10 Dialkylamino, C 3 -C 15 Trialkylammonium, chloride and bromine.

[0048] The term “C 1 -C 6 Alkoxy", "C 2 -C 6 Alkoxycarbonyl" and "C 2 -C 6 "Alkanoyloxy" is used to denote the groups corresponding to the structures -OR 5 , –CO 2 R 5 and –OCOR 5 A group in which R 5 is substituted or unsubstituted C 1 -C 6 alkyl.

[0049] The term "C 1-C 15 Aminocarbonyl" and "C 1 -C 15 The term "amide" is used to denote the groups corresponding to the structures -NHCOR 6 and –CONHR 6 A group in which R 6 is substituted or unsubstituted C 1 -C 15 alkyl.

[0050] The term "C 3 -C 8 "Cycloalkyl" is used to denote a saturated carbocyclic hydrocarbon radical having three to eight carbon atoms.

[0051] R 1 The hydrocarbon group may be branched or straight chain; substituted or unsubstituted; and saturated, monounsaturated, or polyunsaturated C 1 -C 8 In one embodiment, R 1 is substituted or unsubstituted C 3 -C 8 Cycloalkylene.

[0052] In a preferred embodiment, R 1 Selected from branched or straight chain C 1 -C 8 Alkylene, branched or straight chain C 2 -C 8 Alkenylene, and substituted or unsubstituted C 3 -C 8 In another preferred embodiment, R 1 and R 2 Combine to form C 3 -C 8 Saturated, monounsaturated or polyunsaturated ring structure.

[0053] R 1 The divalent hydrocarbon group may be substituted by one to five substituents selected from the following: 1 -C 6 Alkoxy, C 1 -C 6 Carboxyl, C 1 -C 15 Aminocarbonyl, C 1 -C 15 Amide, cyano, C 2 -C 6 Alkoxycarbonyl, C 2 -C 6 Alkanoyloxy, hydroxy, aryl, heteroaryl, thioether, C 2-C 10 Dialkylamino, C 3 -C 15 Trialkylammonium, chloride and bromine.

[0054] In one embodiment, R is greater than R 1 At least two more carbon atoms.

[0055] By R 2 and R 3 The groups represented may be substituted or unsubstituted and branched or straight-chain.

[0056] R 2 and R 3 Each independently may be substituted by one to three substituents selected from the following: 1 -C 6 Alkoxy, carboxyl, C 1 -C 15 Aminocarbonyl, C 1 -C 15 Amide, cyano, C 2 -C 6 Alkoxycarbonyl, C 2 -C 6 Alkanoyloxy, hydroxy, aryl, heteroaryl, thioether, C 2 -C 10 Dialkylamino, C 3 -C 15 Trialkylammonium, chloride and bromine.

[0057] In one embodiment, R 2 and R 3 At least one of is alkyl, alkenyl, diene or triene. 2 and R 3 At least one of them is C 3 -C 8 Cycloalkyl.

[0058] In a preferred embodiment, R 2 and R 3 Selected from linear or branched C 1 -C 6 Alkyl and alkenyl.

[0059] R 1 , R 2 and R 3 At least two of them can be combined with N +The heterocyclic rings (nitrogen-containing) may be saturated, monounsaturated or polyunsaturated and may be mono- or polycyclic structures. Examples of these heterocyclic structures include pyrrolidinium, piperidinium, pyridinium, quinolinium, tetrahydroquinolinium, indolinium, octahydroindolinium, acridinium, octahydroacridinium and tetradecahydroacridinium.

[0060] By R 4 The divalent hydrocarbon radical represented may be straight-chain or branched and may be substituted or unsubstituted.

[0061] R 4 The hydrocarbon group may be substituted by one to three substituents selected from the following: 1 -C 6 Alkoxy, carboxyl, C 1 -C 15 Aminocarbonyl, C 1 -C 15 Amide, cyano, C 2 -C 6 Alkoxycarbonyl, C 2 -C 6 Alkanoyloxy, hydroxy, aryl, heteroaryl, thioether, C 2 -C 10 Dialkylamino, C 3 -C 15 Trialkylammonium, chloride and bromine.

[0062] In a preferred embodiment, R 4 is selected from substituted or unsubstituted C 1 -C 8 Alkylene.

[0063] Preferred examples of the compounds of the present invention include those represented by Formula 1, wherein R is selected from C 5 -C 19 Alkyl, C 5 -C 17 Alkenyl, C 5 -C 17 Diene and C 3 -C 8 Cycloalkyl; R 1 Selected from C 1 -C 8 Alkylene, C 2 -C 8 Alkenylene and C 3 -C 8 Cycloalkylene; R 2 and R 3 Each independently selected from C 1 -C 6 Alkyl and C 1 -C 6Alkenyl; R 1 and R 2 Can be used with N + Connect to form C 3 -C 8 heterocyclic structure; and R 4 is substituted or unsubstituted C 1 -C 8 Alkylene.

[0064] Preferred examples of the compounds of the present invention also include those represented by Formula 1, wherein RCO- is C 6 To C 20 Acyl groups such as octanoyl, decanoyl and lauroyl; R 1 is ethylene, 1,3-propylene or 1,3-butylene; R 2 and R 3 is methyl; and R 4 It is ethylene, 1,3-propylene, 1,4-butylene or 2-hydroxy-1,3-propylene.

[0065] Preferred examples of the compounds of the present invention further include those represented by Formula 1, wherein RCO- is C 6 To C 20 acyl groups such as octanoyl, decanoyl and lauroyl; and R 1 and R 2 With N + connected to form 3-piperidinium, 4-piperidinium, 3-piperidiniummethyl, 4-piperidiniummethyl, 3-pyridinium, 4-pyridinium, 3-pyridiniummethyl or 4-pyridiniummethyl; R 3 is methyl; and R 4 It is ethylene, 1,3-propylene, 1,4-butylene or 2-hydroxy-1,3-propylene.

[0066] In various embodiments of the present invention, "C 6 To C 20 The "acyl group" may be derived from coconut oil, hydrogenated coconut oil, hydrogenated and / or fractionated coconut fatty acids, palm kernel oil, hydrogenated palm kernel oil, or hydrogenated and / or fractionated palm kernel fatty acids. In this case, the resulting product may be a mixture of two or more compounds of Formula 1, each having a different R substituent. For example, "C 6 To C 20 The "acyl" group may be derived from hydrogenated and stripped / fractionated coconut fatty acids. Coconut fatty acids typically include fatty acids such as C 8 , C 10 , C 12 , C 14 , C 16 and C 18A mixture of fatty acids. The fatty acids may be saturated, monounsaturated or polyunsaturated. The mixture may be hydrogenated to increase its melting point. In addition, the mixture may be stripped, for example, of medium chain fatty acids, such as C 8 To C 10 Fatty acids, to produce a major amount of long-chain fatty acids, such as C 12 - C 18 These fractions (medium chain or long chain, for example) can be used to produce the compounds of the present invention. When such fractions are used, the reaction product includes a mixture of compounds of formula 1, some of which may have, for example, C 12 acyl substituents, while other compounds may have C 14 Acyl substituents, etc.

[0067] Therefore, in another aspect, the present invention provides a mixture comprising at least two compounds having formula 1:

[0068]

[0069] in

[0070] R is C 3 -C 23 Hydrocarbon;

[0071] R 1 C 1 -C 8 Hydrocarbon;

[0072] R 2 and R 3 Each independently selected from C 1 -C 6 Alkyl, C 1 -C 6 Alkenyl, C 1 -C 6 Dienyl, C 1 -C 6 Triene and C 3 -C 8 Cycloalkyl;

[0073] Where R 1 , R 2 and R 3 At least two of them can be combined with N + connected to form a heterocyclic ring; and

[0074] R 4 C 1 -C 8 The at least two compounds have at least one different R substituent. In other words, the at least two compounds have different R substituents.

[0075] Preferred examples of the compounds in the mixture according to the present invention include those represented by Formula 1, wherein RCO- is C 6 To C 20 Acyl groups such as caprylyl, capryl, cocoyl (acyl groups derived from coconut fatty acids), hydrogenated cocoyl (acyl groups derived from hydrogenated coconut fatty acids), and hydrogenated stripped cocoyl (acyl groups derived from hydrogenated and fractionated / stripped coconut fatty acids); R 1 is ethylene, 1,3-propylene or 1,3-butylene; R 2 and R 3 is methyl; and R 4 It is ethylene, 1,3-propylene, 1,4-butylene or 2-hydroxy-1,3-propylene.

[0076] Preferred examples of the compounds in the mixture according to the present invention also include those represented by Formula 1, wherein RCO- is C 6 To C 20 Acyl groups such as caprylyl, capryl, cocoyl (acyl groups derived from coconut fatty acids), hydrogenated cocoyl (acyl groups derived from hydrogenated coconut fatty acids), and hydrogenated stripped cocoyl (acyl groups derived from hydrogenated and fractionated / stripped coconut fatty acids); R 1 and R 2 With N + connected to form 3-piperidinium, 4-piperidinium, 3-piperidiniummethyl, 4-piperidiniummethyl, 3-pyridinium, 4-pyridinium, 3-pyridiniummethyl or 4-pyridiniummethyl; R 3 is methyl; and R 4 It is ethylene, 1,3-propylene, 1,4-butylene or 2-hydroxy-1,3-propylene.

[0077] In another aspect, the present invention provides a method for preparing amphoteric ester sulfonate. The method comprises:

[0078] (a) contacting an acid or ester of Formula 2 with a dialkylamino alcohol of Formula 3 in the presence of an enzyme under conditions effective to form an intermediate of Formula 4:

[0079]

[0080]

[0081] Among them, R 1 , R 2 and R 3 As defined above, R 7 is hydrogen or C 1 -C 6 Alkyl; and

[0082] (b) contacting the intermediate of formula 4 with a sulfonate alkylating agent under conditions effective to form a compound of formula 1.

[0083] The carboxylic acid or ester of formula 2 can be obtained commercially or can be produced by any practical method known in the art, including hydrolysis or solvolysis of triglycerides in the presence of water or lower alcohol and base, acid, or enzyme catalyst. 1 -C 4 Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and isobutanol.

[0084] The first step of the process involves the reaction of a dialkylamino alcohol of Formula 3 with an acid or ester of Formula 2 in the presence of an enzyme to form the desired intermediate of Formula 4.

[0085] The enzyme reaction of step (a) can be carried out in the absence of an additional solvent or in the presence of an inert solvent. Examples of inert solvents include cyclic or noncyclic ether solvents (e.g., diethyl ether, diisopropyl ether, tert-butyl methyl ether, and tetrahydrofuran), aromatic hydrocarbons (e.g., benzene, toluene, and xylene), aliphatic or alicyclic saturated or unsaturated hydrocarbons (e.g., hexane, heptane, cyclohexane, and limonene), halogenated hydrocarbons (e.g., dichloromethane, dichloroethane, dibromoethane, tetrachloroethylene, and chlorobenzene), polar aprotic solvents (e.g., acetonitrile, dimethylformamide, and dimethyl sulfoxide), and mixtures thereof.

[0086] In one embodiment, the enzymatic reaction is performed in the absence of additional solvent.

[0087] In another embodiment, the enzymatic reaction is carried out in the presence of one or more aliphatic hydrocarbons as solvent.

[0088] The enzyme reaction can be carried out at a temperature of about -100° C. to the boiling point of the solvent (if used), preferably about 20 to 80° C., and more preferably 50 to 70° C. The amount of the dialkylamino-alcohol 3 can be 0.85 to 20 equivalents based on the fatty acid or ester 2, preferably 1 to 10 equivalents, and more preferably 1 to 1.5 equivalents.

[0089] Step (a) of the method of the present invention is desirably carried out in the presence of an enzyme effective for reacting the fatty acid or ester 2 with the dialkylamino-alcohol 3 to form the intermediate compound of formula 4. Effective enzymes for this reaction include lipases. Examples of these enzymes include, but are not limited to, Lipase PS (from Pseudomonas species ( Psuedomonas sp )), Lipase PS-C (from Pseudomonas species immobilized on ceramic), Lipase PS-D (from Pseudomonas species immobilized on diatomaceous earth), Lipoprime 50T, Lipozyme TL IM, Novozyme 435 (from Candida antarctica immobilized on acrylic resin Candida antarctica ) lipase) and Candida antarctica lipase B immobilized on a porous fluoropolymer support, as described in US 2012 / 0040395 A1. The immobilized enzyme has the advantage of being easily removed from the product and reused.

[0090] The enzyme reaction can be carried out with or without the removal of in-situ water or alcohol byproducts. The water or alcohol byproducts can be removed by any known technology, for example chemically by alcohol or water absorbents (such as molecular sieves) or by physical separation (such as evaporation). The byproduct removal is preferably carried out by evaporation, by adopting an inert gas such as nitrogen, argon or helium to purge the reaction mixture or by carrying out the reaction under reduced pressure or both, and these conditions can obtain a> 98% conversion rate of fatty acid or ester 2 to intermediate 4. The preferred pressure range for carrying out the reaction is 1 Torr (133.3 Pa) to ambient pressure, more preferably 10 Torr (1,333 Pa) to ambient pressure, and most preferably 50 Torr (6,665 Pa) to ambient pressure. Any organic solvent included in this step may or may not be removed with alcohol or water. After completing the reaction in step (a), the intermediate 4 of the method can be separated using methods known to those skilled in the art, such as extraction, filtration or crystallization.

[0091] The second step in the process to produce the final product of Formula 1 involves reacting the intermediate compound of Formula 4 with a sulfonate alkylating agent. This step can also be carried out without additional solvent or in the presence of a solvent. Examples of solvents include water, alcohols and glycols (e.g., methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, tert-amyl alcohol, ethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol), cyclic or noncyclic ethers (e.g., diethyl ether, diisopropyl ether, tert-butyl methyl ether, and tetrahydrofuran), ether-alcohols (e.g., 2-methoxyethanol, 1-methoxy-2-propanol, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether), aromatic hydrocarbons (e.g., benzene, toluene, and xylene), aliphatic or alicyclic saturated or unsaturated hydrocarbons (e.g., hexane, heptane, cyclohexane, and limonene), halogenated hydrocarbons (e.g., dichloromethane, dichloroethane, dibromoethane, tetrachloroethylene, and chlorobenzene), polar aprotic solvents (e.g., acetonitrile, dimethylformamide, and dimethyl sulfoxide), and mixtures thereof. Preferred solvents include water, C 2 -C 5 Alcohols, ether-alcohols and mixtures thereof.

[0092] The second step may be carried out at a temperature from about -100°C to the boiling point of the solvent (if used), preferably about 25 to 150°C, more preferably 50 to 150°C, most preferably 50 to 125°C.

[0093] The reaction in the second step can be carried out under a wide range of pressures. For example, the pressure range can be from atmospheric pressure to superatmospheric pressure, such as 5 atmospheres or higher.

[0094] The amount of the sulfonate alkylating agent that can be used is not particularly limited. For example, the sulfonate alkylating agent can be used in an amount of 0.75 to 20 equivalents, preferably 1 to 10 equivalents, and more preferably 1 to 1.5 equivalents, based on the intermediate 4.

[0095] Optionally, a base is included in the reaction mixture of step (b). If included, the base can be selected from metal hydroxides, metal carbonates and metal bicarbonates. Preferred bases include sodium carbonate and sodium bicarbonate. The amount of the base used can be 0 molar equivalents to 1 molar equivalent, based on the ester of formula 4. The preferred amount is an amount sufficient to keep the reaction mixture slightly alkaline, generally 7.2 or greater pH.

[0096] Examples of sulfonate alkylating agents include, but are not limited to, 1,3-propane sultone, 1,4-butane sultone, sodium 2-chloroethane sulfonate, and sodium 3-chloro-2-hydroxypropane sulfonate.

[0097] After completion of the reaction in step (b), the intermediate 4 and product 1 of the process can be isolated using methods known to those skilled in the art such as extraction, filtration or crystallization.

[0098] The method of the present invention can be used to prepare a mixture of two or more compounds of formula 1. If desired, a mixture of two or more carboxylic acids or esters of formula 2 can be used in the enzyme reaction step. Such mixtures can be derived from coconut oil, hydrogenated coconut oil, hydrogenated and / or fractionated coconut fatty acids, palm kernel oil, hydrogenated palm kernel oil, or hydrogenated and / or fractionated palm kernel fatty acids. The enzyme reaction step obtains a mixture of intermediates of formula 4. The mixture of intermediates 4 can then react with a sulfonate alkylating agent to produce a mixture of compounds of formula 1.

[0099] The amphoteric ester sulfonates of formula 1 are particularly useful as surfactants. Therefore, another aspect of the present invention relates to a composition of matter comprising one or more compounds of formula 1 as surfactants. The composition may contain 0.001 to 20% by weight of the compound of formula 1.

[0100] In particular, the amphoteric ester sulfonates of the present invention have hydrophilic and hydrophobic regions, making them useful as surfactants in a wide variety of formulated product applications including personal care products, such as skin care, hair care and other cosmetic products; household and industrial surface cleaners; laundry products; dishwashing detergents; disinfectants; metalworking compositions; rust inhibitors; lubricants; oilfield supplies; oil dispersants; agricultural chemicals; and dye dispersants. The amphoteric ester sulfonates can also be used as emulsifiers and thickeners in emulsions. The amphoteric ester sulfonates can be formulated into products as primary or secondary surfactants. Despite their primary use as wetting agents and foaming agents, amphoteric ester sulfonates can also be used for their antistatic and viscosity control properties.

[0101] Such formulated products may contain from about 0.001% to about 20%, from about 0.01% to about 15%, or even from about 0.1% to about 10% by weight of the amphoteric ester sulfonate.

[0102] In addition to the amphoteric ester sulfonates, the formulated products of the present invention may also contain other surfactants. These other surfactants may include anionic surfactants (e.g., alcohol ether sulfates, linear alkylbenzene sulfonates, and acyl isethionates), cationic surfactants (e.g., quaternary ammonium salts, amine oxides, and ester quaternary compounds), amphoteric surfactants (e.g., betaines, amidobetaines, ester betaines, and amphoteric acetates), and nonionic surfactants (e.g., alkyl polyglycosides, alcohol ethoxylates, and fatty alcohol amides). Such ingredients are known to those skilled in the art.

[0103] As stated, the formulated products of the present invention may be cosmetic skin and hair care compositions. In addition to the amphoteric ester sulfonates, those compositions may also contain skin conditioning ingredients or cosmetically acceptable carriers.

[0104] Such skin care ingredients / carriers include retinol, retinyl esters, tetronic acid, tetronic acid derivatives, hydroquinone, kojic acid, gallic acid, arbutin, alpha-hydroxy acids, niacinamide, pyridoxine, ascorbic acid, vitamin E and derivatives, aloe vera, salicylic acid, benzoyl peroxide, witch hazel, caffeine, zinc pyrithione, and fatty acid esters of ascorbic acid. Other skin care ingredients and carriers are known to those skilled in the art and can be used in the compositions of the present invention.

[0105] Additional ingredients that may be included in these formulations include conditioning agents (e.g., polyquaternium salts and panthenol), pearlescent agents (e.g., glycol distearate, distearyl ether, and mica), UV filters (e.g., octocrylene, octyl methoxycinnamate, benzophenone-4, titanium dioxide, and zinc oxide), exfoliating additives (e.g., almond seeds, walnut shells, polymer beads, and pumice), silicones (e.g., dimethicone, cyclomethicone, and amodimethicone), moisturizers (e.g., petrolatum, sunflower oil, fatty alcohols, and shea butter), foam stabilizers (e.g., cocamide MEA and cocamide DEA), antimicrobial agents such as triclosan, humectants such as glycerin, thickeners (e.g., guar gum, sodium chloride, and carbomer), hair and skin damage repair agents (e.g., proteins, hydrolyzed proteins, and hydrolyzed collagen), and foam boosters such as cocamide MIPA. Such additional ingredients are known to those skilled in the art and may be used in the compositions of the present invention.

[0106] Many personal care products are known in the art. They typically include acceptable carriers (e.g., water, oil and / or alcohol), emollients (e.g., olive oil, hydrocarbon oil and wax, silicone oil, other plants, animals or marine fats or oils, glyceride derivatives, fatty acids or fatty acid esters), alcohols or alcohol ethers, lecithin, lanolin and derivatives, polyhydroxy alcohols or esters, wax esters, sterols, phospholipids, etc. These same general ingredients can be formulated into liquids (e.g., liquid soaps, shampoos or shower gels), facial creams, lotions, gels, or solid sticks by using the described ingredients of different proportions and / or by comprising thickeners such as gums or other forms of hydrophilic colloids. All such products can include amphoteric ester sulfonates of the present invention.

[0107] As used herein, the indefinite articles "a" and "an" refer to one or more, unless the context clearly indicates otherwise. Similarly, singular forms of nouns include their plural forms and vice versa, unless the context clearly indicates otherwise.

[0108] Although attempts have been made to set forth with certainty, the values ​​and ranges described herein should be considered approximate (even when not limited by the term "about"). These values ​​and ranges may vary from the values ​​for which they are described, depending on the desired properties sought to be obtained by the present invention and the variations obtained from the standard deviations present in the measurement techniques. In addition, the ranges described herein are required and specifically contemplated to include all subranges and values ​​within the described ranges. For example, a range of 50 to 100 is intended to be described, including all values ​​within that range (including subranges such as 60 to 90 and 70 to 80).

[0109] The contents of all documents cited herein, including patent and non-patent literature, are incorporated herein by reference in their entirety. In the event that any introduced subject matter conflicts with any disclosure herein, the disclosure herein shall take precedence over the introduced content.

[0110] The present invention can be further illustrated by the following examples of preferred embodiments thereof, however it will be understood that these examples are included for illustrative purposes only and are not intended to limit the scope of the present invention. Example

[0111] Example 1

[0112] Preparation of Methyl Cocoate

[0113] Potassium hydroxide (1 g) and methanol (25 g) were added to the tank. The solution was stirred for 1 hour. Coconut oil (100 g) was added to a separate tank. The solid was heated to melt and the KOH / MeOH solution was added and the mixture was stirred overnight. The mixture was transferred to a separatory funnel and separated. The bottom / glycerol layer was removed. The top layer was filtered to obtain a light yellow oil (100 g). 1 H NMR (300 MHz, CDCl 3 ) δ 3.65 (s, 3H), 2.28 (t, 2H), 1.60 (m, 2H), 1.24 (s, 16H), 0.86 (t, 3H).

[0114] Example 2

[0115] Preparation of 3-dimethylaminopropyl citrate

[0116] Methyl citrate (8.72 g, 38.5 mmol), dimethylaminopropanol (4.76 g, 46.2 mmol, 1.2 eq) and Novozym 435 (400 mg) were added to a 50-mL conical bottom plastic vial. The syringe was inserted through the cap and two additional holes were poked for gas to leave. Nitrogen was bubbled at a rate sufficient to mix the contents. The vial was placed in a heater set to 65°C. The reaction was monitored by GC / MS to observe the disappearance of the starting material. After approximately 24 hours, the reaction was complete. The reaction mixture was cooled. Novozym 435 was removed by filtration to obtain the product (9.2 g; 67% yield) in the form of a light yellow oil without further purification. 1 H NMR (300 MHz, CDCl 3) δ 4.10 (t, 2H), 2.30 (m,4H), 2.21 (s, 6H), 1.78 (t, 2H), 1.60 (m, 2H), 1.24 (s, 16H), 0.86 (t, 3H).

[0117] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changing to 100% methanol over 1 min, maintained at 100% methanol for 9 min, ELSD detection): t R (laurate) 4.6 min.

[0118] Example 3

[0119] Preparation of 3-(Cocoyloxypropyldimethylammonium)-2-hydroxypropanesulfonate

[0120] Coconut oil 3-dimethylaminopropyl ester (10 g, 33.5 mmol), sodium 2-hydroxy-3-chloropropanesulfonate (about 90 wt%; 7.68 g, 35.2 mmol, 1.05 eq), sodium carbonate (355 mg; 3.35 mmol; 0.10 eq), isopropanol (10 mL) and water (10 mL) were added to a 250-mL round bottom flask with a magnetic stir bar and condenser. The reaction mixture was heated in a 90°C oil bath for 18 hours to obtain 99.5 area % conversion according to HPLC analysis. The mixture was concentrated under reduced pressure to 28.31 g. Water (23 g) was added, the mixture was heated to obtain a solution, the mixture was placed in a 65°C oil bath, and the head space was purged with nitrogen (1500 mL / min) for 2 hours to remove the remaining isopropanol to a weight of 33.78 g. Water (17.5 g) was added and the mixture was stirred at 65° C. for 10 minutes to obtain a homogeneous solution. The total weight of the solution was 51.11 g, indicating a 29 wt % solution of 3-(cocoyloxypropyldimethylammonio)-2-hydroxypropanesulfonate in water. 1 H NMR analysis was consistent with the product structure.

[0121] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changed to 100% methanol over 1 min, maintained at 100% methanol for 9 min, ELSD detection): t R (lauric acid ester) 4.9 min.

[0122] Example 4

[0123] Preparation of 3-(Cocoyloxypropyldimethylammonium)propanesulfonate

[0124] Coconut oil 3-dimethylaminopropyl ester (5 g, 16.7 mmol), 1,3-propane sultone (2.045 g, 16.7 mmol, 1.0 eq) and water (16.4 g) were added to a 100-mL round-bottom flask with a magnetic stirring bar and a condenser. The reaction mixture was stirred at ambient temperature for 21 hours to obtain 98.2 area % conversion according to HPLC analysis. The gross weight of the solution was 23.4 g, indicating a 29.6 wt% solution of 3-(cocoyloxypropyl dimethylammonio) propane sulfonate in water. 1 HNMR analysis was consistent with the product structure.

[0125] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changed to 100% methanol over 1 min, maintained at 100% methanol for 9 min, ELSD detection): t R (lauric acid ester) 4.8 min.

[0126] Example 5

[0127] Preparation of 1-dimethylamino-2-propyl coconut oil

[0128] Methyl cocoate (35 g, 160 mmol), 1-dimethylamino-2-propanol (16.49 g, 160 mmol, 1.0 eq) and Novozym 435 (2.62 g) were added to a 250-mL 3-neck round-bottom flask. The mixture was heated to 50 °C with stirring and purged with nitrogen (500 mL / min). The GC and 1 The reaction was monitored by H NMR and additional 1-dimethylamino-2-propanol (lost due to evaporation) was added as needed until >99 mol% conversion was achieved. The enzyme was removed by filtration and the solids were washed with toluene. The filtrate was concentrated to obtain 1-dimethylamino-2-propyl cocoate (42.66 g; 94% yield). 1 H NMR (300 MHz, CDCl 3 ) δ 5.06 (m(6), 1H), 2.51 (dd, 1H), 2.31 (m, 3H); 2.26 (s,6H), 1.60 (m, 2H), 1.22 (s, 16H), 0.88 (t, 3H).

[0129] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changing to 100% methanol over 1 min, maintaining at 100% methanol for 9 min, ELSD detection): t R (laurate) 4.6 min.

[0130] Example 6

[0131] Preparation of 3-(2-(cocoyloxy)propyldimethylammonium)-2-hydroxypropanesulfonate

[0132] 1-Dimethylamino-2-propyl cocoate (5.0 g, 16.7 mmol), sodium 2-hydroxy-3-chloropropanesulfonate (about 90 wt%; 3.84 g, 17.6 mmol, 1.05eq), sodium carbonate (177 mg; 1.67 mmol; 0.10 eq), isopropanol (5 mL) and water (5 mL) were added to a 250-mL round-bottom flask with a magnetic stirring bar and a condenser. The reaction mixture was heated in a 90°C oil bath for 32 hours to provide a 98.7 area % conversion according to HPLC analysis. The mixture was concentrated under reduced pressure and water (23 g) was added. The mixture was heated to provide a solution, and the mixture was placed at ambient temperature and the headspace was purged to a small volume with nitrogen (1000 mL / min). The mixture was reconstituted with 10 mL of isopropanol and 4 mL of water to provide a clear solution. The total weight was 23.41 g, which represented an approximately 31% solution of 3-(2-(cocoyloxy)propyldimethylammonio)-2-hydroxypropanesulfonate in isopropanol / water. 1 H NMR analysis was consistent with the product structure.

[0133] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changed to 100% methanol over 1 min, maintained at 100% methanol for 9 min, ELSD detection): t R (laurate) 5.3 min.

[0134] Example 7

[0135] Preparation of Dimethylaminoethyl Cocoate

[0136] Coconut ethyl ester (10 g, 38.5 mmol), dimethylaminoethanol (5.09 g, 57.7 mmol, 1.5 eq) and Novozym 435 (400 mg) were added to a 50-mL conical bottom plastic vial. The syringe was inserted through the cap and two additional holes were poked for the gas to leave. Nitrogen was bubbled at a rate sufficient to mix the contents. The vial was placed in a heating block set at 65°C. The reaction was monitored by GC / MS to observe the disappearance of the starting material. The reaction was completed after approximately 24 hours. The reaction mixture was cooled. Novozym 435 was removed by filtration to provide the product (8 g; 73% yield) in the form of a light yellow oil without further purification. 1 H NMR (300 MHz, CDCl 3 ) δ 4.15 (t, 2H), 2.54 (t, 2H), 2.31 (t, 2H), 2.26 (s, 6H), 1.60 (m, 2H), 1.24 (s, 16H), 0.86 (t, 3H).

[0137] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changing to 100% methanol over 1 min, maintaining at 100% methanol for 9 min, ELSD detection): t R (lauric acid ester) 4.2 min.

[0138] Example 8

[0139] Preparation of 3-(Cocoyloxyethyldimethylammonium)-2-hydroxypropanesulfonate

[0140] Coconut oil 2-dimethylaminoethyl ester (5.0 g, 17.6 mmol), sodium 2-hydroxy-3-chloropropanesulfonate (about 90 wt%; 4.41 g, 20.2 mmol, 1.15 eq), sodium carbonate (186 mg; 1.76 mmol; 0.10 eq), isopropanol (5 mL) and water (5 mL) were added to a 100-mL round-bottom flask with a magnetic stirring bar and condenser. The reaction mixture was heated in a 90°C oil bath for 18 hours to provide a 95.3 area % conversion according to HPLC analysis. The mixture was concentrated with a headspace purge and diluted with water to about 30% concentration to provide a multiphase mixture. The material was concentrated with a headspace nitrogen purge at 60°C and reconstituted with isopropanol and water to provide a clear solution. The total weight was 26.10 g, which represented an approximately 27% solution of 3-(cocoyloxyethyldimethylammonio)-2-hydroxypropanesulfonate in isopropanol / water.1 H NMR analysis was consistent with the product structure.

[0141] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changed to 100% methanol over 1 min, maintained at 100% methanol for 9 min, ELSD detection): t R (laurate) 4.6 min.

[0142] Example 9

[0143] Preparation of 3-(Cocoyloxypropyldimethylammonium)butanesulfonate

[0144] To a 250-mL round bottom flask with a magnetic stir bar and condenser was added 3-dimethylaminopropyl cocoate (10.0 g, 33.5 mmol), 1,4-butane sultone (4.56 g, 33.5 mmol, 1.0 eq), isopropanol (10 mL) and water (10 mL). The reaction mixture was stirred and heated at 80° C. for 24 hours to provide 99.1 area % conversion according to HPLC analysis. The total weight of the solution was 31.27 g, indicating an approximately 46 wt % solution of 3-(cocoyloxypropyldimethylammonio)butane sulfonate in isopropanol / water. 1 H NMR analysis was consistent with the product structure.

[0145] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changing to 100% methanol over 1 min, maintaining at 100% methanol for 9 min, ELSD detection): t R (laurate) 4.75 min.

[0146] Example 10

[0147] Preparation of 3-(Cocoyloxyethyldimethylammonium)propanesulfonate

[0148] Coconut oil 2-dimethylaminoethyl ester (3.5 g, 12.3 mmol), 1,3-propane sultone (1.50 g, 12.3 mmol, 1.0 eq), isopropanol (3.5 mL) and water (3.5 mL) were added to a 100-mL round-bottom flask with a magnetic stirring bar and a condenser. The reaction mixture was stirred at ambient temperature for 36 hours to provide a 99.3 area % conversion according to HPLC analysis. The gross weight of the solution was 10.87 g, indicating an approximately 46 wt % solution of 3-(cocoyloxyethyldimethylammonio)-propane sulfonate in isopropanol / water. 1 H NMR analysis was consistent with the product structure.

[0149] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changed to 100% methanol over 1 min, maintained at 100% methanol for 9 min, ELSD detection): t R (lauric acid ester) 4.5 min.

[0150] Embodiment 11

[0151] Preparation of N-methyl-4-piperidinyl coconut oil ester

[0152] Methyl cocoate (25 g, 117 mmol), 4-hydroxy-N-methylpiperidine (17.46 g, 152 mmol), heptane (10 mL) and Novozym 435 (2.50 g) were added to a 250-mL round-bottom flask with a magnetic stir bar. A Dean-Stark apparatus was placed on the flask and the mixture was heated to 65°C. The heptane azeotrope was used to remove methanol by reducing the pressure until the azeotrope was distilled overhead into the Dean-Stark water trap to return the heptane to the reaction vessel. After 1.5 hours, the reaction was stopped. After the mixture was cooled to ambient temperature, Novozym 435 was recovered by filtration. After heating to 65°C, nitrogen was bubbled through the mixture to remove any unreacted 4-hydroxy-N-methylpiperidine. 1 H NMR analysis indicated 98 mol % conversion to the product, which was isolated as a yellow oil (29.57 g; 82 % yield). 1 H NMR (300 MHz, CDCl 3) δ 4.78 (m, 1H), 2.66 (m, 2H), 2.32-2.22 (m, 7H); 1.95-1.86 (m, 2H); 1.77-1.58 (m, 4H); 1.38-1.25 (m, 18H), 0.88 (t, 3H).

[0153] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changed to 100% methanol over 1 min, maintained at 100% methanol for 9 min, ELSD detection): t R (lauric acid ester) 4.2 min.

[0154] Example 12

[0155] Preparation of 3-(4-(cocoyloxy)-1-methylpiperidinium-1-yl)-2-hydroxypropanesulfonate

[0156] To a 100-mL round bottom flask with a magnetic stir bar and condenser was added N-methyl-4-piperidinyl cocoate (5.0 g, 16.2 mmol), sodium 2-hydroxy-3-chloropropanesulfonate (approximately 90 wt%; 3.70 g, 16.95 mmol, 1.05 eq), sodium carbonate (171 mg; 1.62 mmol; 0.10 eq), isopropanol (5 mL), and water (5 mL). The reaction mixture was heated in a 90°C oil bath for 24 hours to provide 98.5 area % conversion according to HPLC analysis. The total weight of the solution was 15.50 g, indicating an approximately 46 wt% solution of 3-(4-(cocoyloxy)-1-methylpiperidinium-1-yl)-2-hydroxypropanesulfonate in isopropanol / water. 1 H NMR analysis was consistent with the product structure.

[0157] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changed to 100% methanol over 1 min, maintained at 100% methanol for 9 min, ELSD detection): t R (laurate) 4.9, 5.2 min.

[0158] Embodiment 13

[0159] Preparation of N-methyl-4-piperidinyl methyl coconut oil ester

[0160] Methyl cocoate (50 g, 233 mmol), 4-hydroxymethyl-N-methylpiperidine (33.2 g, 257 mmol) and Novozym 435 (5.0 g) were added to a 250-mL round-bottom flask. The flask was equipped with a septum and a needle was inserted into the outlet. Nitrogen was bubbled at a rate sufficient to mix the contents. The reaction mixture was heated to 50°C. After approximately 15 hours, 1 HNMR analysis indicated that the reaction was complete. The reaction mixture was cooled. Novozym 435 was removed by filtration. The material was taken up in diethyl ether (250 mL) and then washed with water (250 mL x 2). 2 SO 4 After drying, the mixture was filtered and concentrated.After dissolving in a small amount of dichloromethane, the mixture was filtered through a short plug of magnesol and concentrated to afford the product as a light yellow oil (57.89 g; 77% yield). 1 H NMR (300 MHz, CDCl 3 ) δ 3.93(d, 2H), 2.86 (m, 2H), 2.32-2.27 (m, 5H), 1.91 (t, 3H), 1.73-1.56 (m, 5H), 1.41-1.23 (m, 19H), 0.88 (t, 3H).

[0161] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changed to 100% methanol over 1 min, maintained at 100% methanol for 9 min, ELSD detection): t R (lauric acid ester) 4.2 min.

[0162] Embodiment 14

[0163] Preparation of 3-((4-(cocoyloxy)methyl)-1-methylpiperidinium-1-yl)-2-hydroxypropanesulfonate

[0164] To a 100-mL round bottom flask with a magnetic stir bar and condenser was added N-methyl-4-piperidinyl cocoate (4.5 g, 13.9 mmol), sodium 2-hydroxy-3-chloropropanesulfonate (approximately 90 wt%; 3.19 g, 14.6 mmol, 1.05 eq), sodium carbonate (147 mg; 1.39 mmol; 0.10 eq), isopropanol (4.5 mL), and water (4.5 mL). The reaction mixture was heated in a 90°C oil bath for 15 hours to provide complete conversion according to HPLC analysis. The total weight of the solution was 14.20 g, indicating an approximately 45 wt% solution of 3-((4-(cocoyloxy)methyl)-1-methylpiperidinium-1-yl)-2-hydroxypropanesulfonate in isopropanol / water. 1 H NMR analysis was consistent with the product structure.

[0165] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changed to 100% methanol over 1 min, maintained at 100% methanol for 9 min, ELSD detection): t R (laurate) 5.2, 5.5 min.

[0166] Embodiment 15

[0167] Preparation of Dimethylaminopropyl Laurate

[0168] Lauric acid (600 g; 3.0 mol), 3-dimethylaminopropanol (371 g; 3.59 mol; 1.2 eq), Novozym 435 (30 g) and heptane (267 mL) were combined and heated to 65°C. The heptane azeotrope was used to remove water by reducing the pressure until the azeotrope was distilled overhead into the Dean-Stark trap to return the heptane to the reaction vessel. The reaction was continued until GC analysis showed >99 area % conversion of lauric acid to 3-dimethylaminopropyl ester. The enzyme was removed by filtration, and the filtrate was concentrated. The concentrate was purged with nitrogen at 60°C overnight to remove excess 3-dimethylaminopropanol. 1 H NMR (300MHz, CDCl 3 ) δ 4.09 (t, 2H), 2.32 (t, 2H), 2.27 (t, 2H); 2.20 (s, 6H); 1.78 (m(5), 2H); 1.59 (m, 2H), 1.26 (m, 16H), 0.86 (t, 3H).

[0169] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changed to 100% methanol over 1 min, maintained at 100% methanol for 9 min, ELSD detection): t R 4.6 min.

[0170] Example 16

[0171] Preparation of 3-(lauroyloxypropyldimethylammonium)-2-hydroxypropanesulfonate

[0172] To a 100-mL round-bottom flask with a magnetic stir bar and condenser was added lauric acid 3-dimethylaminopropyl ester (5 g, 17.5 mmol), sodium 2-hydroxy-3-chloropropanesulfonate (approximately 90 wt%; 4.40 g, 20.1 mmol, 1.15 eq), sodium carbonate (186 mg; 1.75 mmol; 0.10 eq), isopropanol (15 mL), and water (2.5 mL). The reaction mixture was heated in a 90°C oil bath for 11 hours to provide a 99.9 area % conversion according to HPLC analysis. The material was filtered and the filtrate was concentrated to 11.29 g under reduced pressure. Water (14 g) was added, the mixture was heated to provide a solution, the mixture was placed in a 65°C oil bath, and the headspace was purged with nitrogen to remove the remaining isopropanol to a weight of 16.00 g. Water (6.93 g) was added and the mixture was stirred at 65°C for 10 min to obtain a homogeneous solution. The total weight of the solution was 22.93 g, indicating a 32 wt % solution of 3-(cocoyloxypropyldimethylammonio)-2-hydroxypropanesulfonate in water. 1 H NMR analysis was consistent with the product structure.

[0173] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changing to 100% methanol over 1 min, maintaining at 100% methanol for 9 min, ELSD detection): t R 4.9 min.

[0174] Embodiment 17

[0175] Preparation of N-methyl-4-piperidinyl laurate

[0176] Methyl laurate (25 g, 117 mmol), 4-hydroxy-N-methylpiperidine (17.46 g, 152 mmol), heptane (10 mL) and Novozym 435 (2.50 g) were added to a 250-mL round bottom flask with a magnetic stir bar. A Dean-Stark apparatus was placed on the flask and the mixture was heated to 65°C. The heptane azeotrope was used to remove water by reducing the pressure until the azeotrope was distilled overhead into the Dean-Stark trap to return the heptane to the reaction vessel. After 3 hours, GC analysis showed 98.7 area % conversion. The reaction was cooled to ambient temperature. Novozym 425 was recovered by filtration. The mixture was taken up in diethyl ether (100 mL) and washed with water (100 mL). The reaction mixture was stirred for 2 hours at room temperature. The reaction mixture was stirred for 2 hours at room temperature. The reaction mixture was stirred for 3 hours at room temperature. ... 2 SO 4 The organics were dried.After filtration, the volatiles were removed under reduced pressure to afford a light yellow oil (32.09 g; 92% yield) which solidified upon standing. 1 H NMR (300MHz, CDCl 3 ) δ 4.78 (m, 1H), 2.65 (m, 2H), 2.32-2.22 (m, 7H); 1.95-1.85 (m,3H); 1.77-1.57 (m, 4H); 1.35-1.23 (m, 17H), 0.88 (t, 3H).

[0177] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changing to 100% methanol over 1 min, maintaining at 100% methanol for 9 min, ELSD detection): t R 4.2 min.

[0178] Embodiment 18

[0179] Preparation of 3-(4-(lauroyloxy)-1-methylpiperidinium-1-yl)-2-hydroxypropanesulfonate

[0180] To a 100-mL round-bottom flask with a magnetic stirring bar and a condenser, add lauric acid N-methyl-4-piperidinyl ester (3.0 g, 10.0 mmol), sodium 2-hydroxy-3-chloropropanesulfonate (about 90 wt%; 2.42 g, 11.1 mmol, 1.1 eq), sodium carbonate (107 mg; 1.0 mmol; 0.10 eq), 1-methoxy-2-propanol (9 mL) and water (1.5 mL). Heat the reaction mixture to reflux (102°C oil bath) for 15 hours to provide 99.5 area % conversion according to HPLC analysis. Concentrate the mixture to about half of the initial volume to provide a precipitate. Remove the precipitate by filtration, and wash the filter cake with isopropanol. Strip the filtrate to a small volume and add water (17.2 g). The mixture was heated to 65°C and the headspace was purged with nitrogen for several hours to remove any remaining isopropanol and 1-methoxy-2-propanol to provide 12.22 g of a product mixture. Water was added to provide a total weight of 14.40 g of solution, indicating an approximately 30 wt % solution of 3-(4-(lauroyloxy)-1-methylpiperidinium-1-yl)-2-hydroxypropanesulfonate in water. 1 H NMR analysis was consistent with the product structure.

[0181] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changing to 100% methanol over 1 min, maintaining at 100% methanol for 9 min, ELSD detection): t R 4.7, 5.0 min.

[0182] Embodiment 19

[0183] Preparation of 3-Cocoyloxymethyl-N-methylpiperidine

[0184] To a 250-mL round bottom flask with a magnetic stir bar was added methyl cocoate (69.0 g, 322 mmol), 3-hydroxymethyl-N-methylpiperidine (49.89 g, 386 mmol) and Novozym 435 (10.0 g). The flask was fitted with a septum and a needle was inserted into the outlet. Nitrogen was bubbled at a rate sufficient to mix the contents. The mixture was heated to 65°C. After 12 hours, the purge rate was increased. At 19.5 hours, 1 H NMR analysis indicated that the reaction was complete. After filtration, the mixture was absorbed in Et 2 O (750 mL) and then washed with water (250 mL x2). 2 SO 4The organics were dried.After filtration, the volatiles were removed under reduced pressure to afford the product as a light yellow oil (91.67 g; 88% yield). 1 H NMR (300 MHz, CDCl 3 ) δ 3.98 (m, 1H), 3.86 (m, 1H), 2.80 (m, 2H), 2.28 (t, 2H), 2.25 (s,3H), 2.03-1.82 (m, 2H), 1.72-1.55 (m, 5H), 1.33-1.18 (m, 18H), 0.87 (t, 3H).

[0185] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changing to 100% methanol over 1 min, maintaining at 100% methanol for 9 min, ELSD detection): t R 4.7 min.

[0186] Embodiment 20

[0187] Preparation of 3-(3-cocoyloxymethyl)-1-methylpiperidinium-1-yl)-2-hydroxypropanesulfonate

[0188] To a 100-mL round bottom flask with a magnetic stir bar and condenser was added 3-cocoyloxymethyl-N-methylpiperidine (5.0 g, 16.1 mmol), sodium 2-hydroxy-3-chloropropanesulfonate (approximately 90 wt%; 3.47 g, 15.9 mmol, 1.0 eq), sodium carbonate (107 mg; 1.0 mmol; 0.10 eq), 1-methoxy-2-propanol (15 mL) and water (2.5 mL). The reaction mixture was heated to reflux (102° C. oil bath) for 15.5 hours to provide 99.3 area % conversion according to HPLC analysis. The mixture was cooled to ambient temperature and the solids were removed by filtration. The total weight of the yellow solution was 21.67 g, indicating an approximately 33 wt % solution of 3-(3-(cocoyloxymethyl)-1-methylpiperidinium-1-yl)-2-hydroxypropanesulfonate in 1-methoxy-2-propanol and water. 1 H NMR analysis was consistent with the product structure.

[0189] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changing to 100% methanol over 1 min, maintaining at 100% methanol for 9 min, ELSD detection): tR (laurate) 5.1, 5.4 min.

[0190] Embodiment 21

[0191] Preparation of Hydrogenated Coconut Acid N-Methyl-4-Piperidinyl Ester

[0192] To a round bottom flask with a magnetic stir bar was added hydrogenated methyl cocoate (30.3 g, 134 mmol), 4-hydroxy-N-methylpiperidine (20.0 g, 174 mmol; 1.3 eq), heptane (10.5 mL) and Novozym 435 (3 g). A Dean-Stark apparatus was placed on the flask, the mixture was heated to 65°C, and the reaction was placed under vacuum to distill the methanol / heptane azeotrope (heptane was returned to the flask via the Dean-Stark apparatus). The reaction was carried out until GC analysis indicated 99 area % conversion to the ester. The reaction was cooled to ambient temperature and the solids were removed by filtration (Novozym 435) and washed with heptane. The filtrate was washed with water and washed with Na 2 SO 4 After filtration, the volatiles were removed under reduced pressure to afford the product as a light yellow oil (41.1 g; 99% yield). 1 H NMR analysis was consistent with the product structure.

[0193] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changing to 100% methanol over 1 min, maintaining at 100% methanol for 9 min, ELSD detection): t R 4.2 min (lauric ester).

[0194] Embodiment 22

[0195] Preparation of 3-(4-(hydrogenated coconut oil acyloxy)-1-methylpiperidinium-1-yl)-2-hydroxypropanesulfonate

[0196] Hydrogenated N-methyl-4-piperidinyl cocoate (7.50 g, 24.18 mmol), sodium 2-hydroxy-3-chloropropanesulfonate (about 90 wt%; 5.81 g, 26.6 mmol, 1.1 eq), sodium carbonate (256 mg; 2.42 mol; 0.10 eq) and 1-methoxy-2-propanol (22.5 mL) were added to a 100-mL round-bottom flask with a magnetic stir bar and condenser. The reaction mixture was heated to 110°C for 24 hours to provide a 99.6 area % conversion to the product according to HPLC analysis. The mixture was filtered while being incubated (60°C) to remove any precipitated solids, and the solids were washed with isopropanol. The combined filtrate and washings were concentrated under reduced pressure and vacuum to provide 12.31 g of the product in the form of an off-white solid. A portion (10.89 g) of this material was dried in a vacuum oven to provide 10.12 g of material which was 93.5 wt % 3-(4-(hydrogenated cocoyloxy)-1-methylpiperidinium-1-yl)-2-hydroxypropanesulfonate by HPLC analysis. 1 H NMR analysis was consistent with the product structure.

[0197] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changing to 100% methanol over 1 min, maintaining at 100% methanol for 9 min, ELSD detection): t R 4.7, 5.0 min (lauric acid ester).

[0198] Embodiment 23

[0199] Preparation of Hydrogenated Stripped N-Methyl-4-Piperidinyl Cocoate

[0200] To a round bottom flask with a magnetic stir bar was added hydrogenated stripped coconut fatty acid (29.7 g, 134 mmol), 4-hydroxy-N-methylpiperidine (20.0 g, 174 mmol; 1.3 eq), heptane (10.5 mL) and Novozym 435 (3 g). A Dean-Stark apparatus was placed on the flask, the mixture was heated to 65°C, and the reaction was placed under vacuum with a distilled water / heptane azeotrope (heptane was returned to the flask via the Dean-Stark apparatus). The reaction was carried out until GC analysis indicated 99 area % conversion to the ester. The reaction was cooled to ambient temperature and the solids (Novozym 435) were removed by filtration and washed with heptane. The filtrate was washed with water and washed with Na 2 SO 4After filtration, the volatiles were removed under reduced pressure to afford the product as a light yellow oil (41.1 g; 96% yield). 1 H NMR analysis was consistent with the product structure.

[0201] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changing to 100% methanol over 1 min, maintaining at 100% methanol for 9 min, ELSD detection): t R 4.2 min (lauric ester).

[0202] Embodiment 24

[0203] Preparation of 3-(4-(hydrogenated stripped cocoyloxy)-1-methylpiperidinium-1-yl)-2-hydroxypropanesulfonate

[0204] To a 100-mL round-bottom flask with a magnetic stirring bar and a condenser, hydrogenated stripped cocoyl N-methyl-4-piperidinyl ester (5.00 g, 15.67 mmol), sodium 2-hydroxy-3-chloropropanesulfonate (about 90 wt%; 3.76 g, 17.24mmol, 1.1 eq), sodium carbonate (166 mg; 1.57 mol; 0.10 eq) and 1-methoxy-2-propanol (15 mL) were added. The reaction mixture was heated to 110°C for 12 hours to provide a 99.0 area % conversion to the product according to HPLC analysis. The mixture was filtered while being incubated (60°C) to remove any precipitated solids, and the solids were washed with isopropanol. The combined filtrate and washings were concentrated under reduced pressure and vacuum to provide 7.69 g of the product in the form of an off-white solid. A portion (6.60 g) of this material was dried in a vacuum oven to provide 6.47 g of material which was 96.9 wt % 3-(4-(hydrogenated stripped cocoyloxy)-1-methylpiperidinium-1-yl)-2-hydroxypropanesulfonate by HPLC analysis. 1 H NMR analysis was consistent with the product structure.

[0205] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changing to 100% methanol over 1 min, maintaining at 100% methanol for 9 min, ELSD detection): t R 4.7, 5.0 min (lauric acid ester).

[0206] Embodiment 25

[0207] Preparation of N-methyl-4-piperidinyl decanoate / octanoate

[0208] A 59:41 (w / w) mixture of decanoic acid and octanoic acid (20.8 g, 134 mmol), 4-hydroxy-N-methylpiperidine (20.0 g, 174 mmol; 1.3 eq), heptane (10.5 mL) and Novozym 435 (2 g) were added to a round bottom flask with a magnetic stir bar. A Dean-Stark apparatus was placed on the flask, the mixture was heated to 65°C, and the reaction was placed under vacuum with a distilled water / heptane azeotrope (heptane was returned to the flask via the Dean-Stark apparatus). The reaction was carried out until GC analysis showed 99 area % conversion to the ester. The reaction was cooled to ambient temperature and the solids (Novozym 435) were removed by filtration and washed with heptane. The filtrate was washed with water and Na 2 SO 4 After filtration, the volatiles were removed under reduced pressure to afford the product as a light yellow oil (32.7 g; 97% yield). 1 H NMR analysis was consistent with the product structure.

[0209] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 80:20 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, ELSD detection): t R 1.95 min (decanoate); 2.35 min (octanoate).

[0210] Embodiment 26

[0211] Preparation of 3-(4-(octanoyloxy / decanoyloxy)-1-methylpiperidinium-1-yl)-2-hydroxypropanesulfonate

[0212] To a 100-mL round-bottom flask with a magnetic stirring bar and a condenser, add decanoic acid / octanoic acid N-methyl-4-piperidinyl ester (5.00 g, 19.77 mmol), sodium 2-hydroxy-3-chloropropanesulfonate (about 90 wt%; 4.75 g, 21.75 mmol, 1.1 eq), sodium carbonate (210 mg; 1.98 mol; 0.10 eq) and 1-methoxy-2-propanol (15 mL). The reaction mixture was heated to 110 ° C for 20 hours to provide a 99.0 area % conversion rate to the product according to HPLC analysis. The mixture was cooled to ambient temperature, filtered to remove any precipitated solids, and the solids were washed with isopropanol. The combined filtrate and washings were concentrated under reduced pressure and vacuum to provide 8.26 g of the product in the form of an off-white solid. A portion (6.91 g) of this material was dried in a vacuum oven to provide 6.41 g of material. 1H NMR analysis was consistent with the product structure.

[0213] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 80:20 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, ELSD detection): t R 2.10 min (decanoate); 2.62 min (octanoate).

[0214] Embodiment 27

[0215] Preparation of 3-(3-(lauroyloxy)-1-butyldimethylammonium-1-yl)-2-hydroxypropanesulfonate

[0216] To a 4-L reactor equipped with a mechanical stirrer and a condenser, 1-dimethylamino-3-butyl laurate (419.06 g, 1.40 mol), sodium 2-hydroxy-3-chloropropanesulfonate (approximately 90 wt%; 336 g, 1.54 mol, 1.1 eq), sodium carbonate (14.83 g; 0.14 mol; 0.10 eq), isopropanol (1260 mL) and water (210 mL) were added. The reaction mixture was heated to reflux for 21 hours to provide a 99.7 area % conversion of the product according to HPLC analysis. The mixture was cooled to ambient temperature and filtered to remove any precipitated solids, and the solids were washed with isopropanol. The combined filtrate and washings were concentrated under reduced pressure, and the residue was treated with water (1428 mL), and the mixture was heated to 65 ° C and purged (head space) with nitrogen to remove residual isopropanol. This resulted in 2012 g of 3-(3-(lauroyloxy)-1-butyldimethylammonio-1-yl)-2-hydroxypropanesulfonate being obtained in the form of a 25.9 wt % aqueous solution (in wt %). 1 H NMR analysis was consistent with the product structure.

[0217] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 80:20 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changing to 100% methanol over 1 min, maintaining at 100% methanol for 9 min, ELSD detection): t R 3.78 min.

[0218] Embodiment 28

[0219] Preparation of 3-(3-(hydrogenated coconut oil acyloxy)-1-butyldimethylammonium-1-yl)-2-hydroxypropane sulfonate

[0220] Hydrogenated 1-dimethylamino-3-butyl coconut oil (2.50 g, 8.08 mmol), sodium 2-hydroxy-3-chloropropanesulfonate (about 90 wt%; 1.94 g, 8.88 mmol, 1.1 eq), sodium carbonate (86 mg; 0.81 mol; 0.10 eq), isopropanol (7.5 mL) and water (1.25 mL) were added to a 100-mL round-bottom flask with a magnetic stirring bar and a condenser. The reaction mixture was heated to reflux for 12 hours to provide a 99.9 area % conversion of the product according to HPLC analysis. The mixture was cooled to ambient temperature and filtered to remove any precipitated solids, and the solids were washed with isopropanol. The filtrate and washings combined were concentrated under reduced pressure and vacuum to provide the product in the form of 3.91 g off-white solids. 1 H NMR analysis was consistent with the product structure.

[0221] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 80:20 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changing to 100% methanol over 1 min, maintaining at 100% methanol for 9 min, ELSD detection): t R 3.78 min (lauric ester).

[0222] Embodiment 29

[0223] 3-(3-(hydrogenated stripped cocoyloxy)-1-butyldimethylammonio-1-yl)-2-hydroxypropanesulfonate preparation

[0224] 1-dimethylamino-3-butyl coconut oil (5.00 g, 15.57 mmol), 2-hydroxy-3-chloropropanesulfonic acid sodium (about 90 wt%; 3.74 g, 17.12 mmol, 1.1 eq), sodium carbonate (165 mg; 1.56 mol; 0.10 eq), isopropanol (15 mL) and water (2.5 mL) of the stripping of hydrogenation are added to a 100-mL round-bottom flask with a magnetic stirring bar and a condenser. The reaction mixture is heated to reflux for 12 hours to provide a 99.9 area % conversion of the product according to HPLC analysis. The mixture is cooled to ambient temperature and filtered to remove any precipitated solids and washed with isopropanol solids. The filtrate and washings combined are concentrated under reduced pressure and vacuum to provide the product in the form of a pale solid of 7.60 g. 1 H NMR analysis was consistent with the product structure.

[0225] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 80:20 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, gradually changing to 100% methanol over 1 min, maintaining at 100% methanol for 9 min, ELSD detection): t R 3.78 min (lauric ester).

[0226] Embodiment 30

[0227] Preparation of 3-(3-(octanoyloxy / decanoyloxy)-1-butyldimethylammonium-1-yl)-2-hydroxypropanesulfonate

[0228] Capric acid / octanoic acid 1-dimethylamino-3-butyl ester (2.50 g, 9.81 mmol), 2-hydroxy-3-chloropropanesulfonic acid sodium (about 90 wt%; 2.36 g, 10.79 mmol, 1.1 eq), sodium carbonate (104 mg; 0.98 mol; 0.10 eq), isopropanol (7.5 mL) and water (1.25 mL) are added to a 100-mL round-bottom flask with a magnetic stirring bar and a condenser. The reaction mixture is heated to reflux for 12 hours to provide a 99.8 area % conversion of the product according to HPLC analysis. The mixture is cooled to ambient temperature and filtered to remove any precipitated solids, and the solid is washed with isopropanol. The filtrate and washings combined are concentrated under reduced pressure and vacuum to provide the product in the form of a pale solid of 4.18 g. 1 H NMR analysis was consistent with the product structure.

[0229] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 80:20 (v:v) methanol:water (containing 0.1 vol% trifluoroacetic acid) for 10 min, ELSD detection): t R 2.15 min (decanoate); 2.68 min (octanoate).

[0230] Surfactant properties

[0231] The surfactant properties of compounds of Formula 1 can be determined by a number of tests including the ASTM Foam Height Test and a test for Critical Micelle Concentration.

[0232] The Standard Test Method for Foaming Properties of Surfactants (ASTM 1173-07) was used to determine the foaming properties of the Ester Sulfonate 1 described herein. This method produces foam under low agitation conditions and is generally used for medium and high foaming surfactants. This test collects data on initial foam height and foam decay. Foam decay provides information on foam stability.

[0233] The device for carrying out this test includes a column and a pipette with a jacket. The column with a jacket serves as a receiver, and the pipette delivers the surfactant solution. Prepare a solution of each surfactant. The amphoteric ester sulfonate solution to be tested is added to a receiver (50 mL) and added to a pipette (200 mL). The pipette is placed above the receiver and opened. As the solution falls and contacts with the solution in the receiver, foam is generated. When the pipette is vacant, the time is recorded and the initial foam height is recorded. The foam height is recorded every minute for five minutes. The precise size description for glassware can be found in ASTM 1173-07. The foam height results and typical standards for each ester sulfonate 1 are listed in the following table 1 (0.1% concentration) and 2 (1% concentration).

[0234] The critical micelle concentration (CMC) of each compound was also determined. The CMC is the concentration of surfactant above which micelles are spontaneously formed. The CMC is an important property of a surfactant. At surfactant concentrations lower than the CMC, the surface tension varies greatly with surfactant concentration. At concentrations above the CMC, the surface tension remains essentially constant. A lower CMC indicates that less surfactant is required to penetrate the interface and form micelles. Typical CMC values ​​are less than 1 wt % (10,000 ppm).

[0235] Chattopadhyay and London Analytical Biochemistry , Vol. 139, pp. 408-412 (1984)) is used to obtain the critical micelle concentrations found in Table 3 below. This method uses the fluorescent dye 1,6-diphenyl-1,3,5-hexatriene (DPH) in surfactant solution. The analysis is based on the difference in fluorescence after the dye is introduced into the interior of the micelle. As the solution exceeds the CMC, a large increase in fluorescence intensity is observed. This method has been found to be sensitive and reliable and has been demonstrated for zwitterionic, anionic, cationic and uncharged surfactants.

[0236] Table 1

[0237] Foam height (cm) at 0.1 wt% concentration at time t (min)

[0238]

[0239] ND = not determined.

[0240] Table 2

[0241] Foam height at 1.0 wt% concentration at time t (min) (cm)

[0242]

[0243] ND = not determined.

[0244] As indicated by the data in Tables 1 and 2, solutions of Amphoteric Ester Sulfonate 1 produced a large amount of foam. Examples in which the foam height did not decrease over time indicated good foam stability.

[0245] Table 3

[0246] Critical micelle concentration

[0247]

[0248] The data in Table 3 indicate that very low concentrations of amphiphilic ester sulfonate 1 are required to reach the critical micelle concentration. These values ​​fall within the range of available surfactants and compare well with standard surfactants.

[0249] stability

[0250] It has been unexpectedly found that the amphoteric ester sulfonates of the present invention are significantly more stable under low pH aqueous conditions than the corresponding amphoteric ester betaines disclosed in US 2012 / 0277324 A1. The amphoteric ester sulfonates exhibit little loss of amphoteric surfactant under extended incubation in pH 4.5 water at 50°C, whereas the similar ester betaines show significant analytical loss of amphoteric surfactant, even under less severe conditions.

[0251] Comparative Example 1

[0252] Preparation of 3-(Cocoyloxypropyldimethylammonium) acetate

[0253] Coconut oil 3-dimethylaminopropyl ester (350.42g; 1.21 mol), sodium chloroacetate (155 g, 1.33 mol, 1.1 eq), sodium bicarbonate (20.32 g; 0.24mol; 0.2 eq) and water (807 g) were added to a 3-L reactor equipped with a condenser and an overhead stirrer. The reaction mixture was stirred and heated to an internal temperature of 76°C for 12 hours to provide a>98% conversion rate according to HPLC analysis. The mixture was cooled to ambient temperature and the pH was adjusted to 6.5 by adding 3 M HCl. The resulting mixture was clarified to provide 1267 g of a clear yellow liquid. Analysis of the mixture by HPLC showed a solution of 29.6 wt% of 3-(cocoyloxypropyl dimethylammonium) acetate in water. 1 H NMR analysis was consistent with the product structure.

[0254] HPLC (150 x 4.6 mm Zorbax SB-C8 column, 80:20 methanol:water (containing 0.1% trifluoroacetic acid) for 10 min, gradually changed to 100% methanol over 1 min, maintained at 100% methanol for 9 min, ELSD detection): t R (lauric acid ester) 3.5 min.

[0255] Embodiment 31

[0256] Study on the Stability of 3-(Lauroyloxypropyldimethylammonium)-2-Hydroxypropanesulfonate

[0257] The product from Example 16 (20 mL) was combined with 210 mg of citric acid hydrate and the pH was lowered to 4.5 by adding aqueous HCl. The resulting mixture was placed in a 50°C oven. Samples were taken periodically and analyzed by quantitative HPLC for the amount of 3-(lauroyloxypropyldimethylammonio)-2-hydroxypropanesulfonate remaining. The results are reported in Table 4 below.

[0258] Comparative Example 2

[0259] Study on the Stability of 3-(Cocoyloxypropyldimethylammonium) Acetate

[0260] The product of Comparative Example 1 was adjusted to pH 5 by addition of aqueous HCl and then placed in a 45°C oven. Samples were taken periodically and analyzed by quantitative HPLC for the amount of 3-(cocoyloxypropyldimethylammonio)acetate remaining. The results are reported in Table 4 below.

[0261] Table 4

[0262] Comparative Stability of Ester Carboxyl and Ester Sulfonate Amphoteric Surfactants

[0263]

[0264] ND = not determined.

[0265] The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that modifications and variations can be effected within the spirit and scope of the invention.

Claims

1. A method for preparing a compound having formula 1: in R is selected from C5-C 19 Alkyl, C5-C 17 Alkenyl and C5-C 17 Dienyl; R 1 is 1,3-butylene; R 2 and R 3 are each independently selected from C1-C6 alkyl and C1-C6 alkenyl; and R 4 is 2-hydroxy-1,3-propylene, The method comprises: (a) contacting an acid or ester of Formula 2 with a dialkylamino alcohol of Formula 3 in the presence of an enzyme under conditions effective to form an intermediate of Formula 4: Among them, R 1 , R 2 and R 3 As defined above, R 7 is hydrogen or C1-C6 alkyl; and (b) contacting the intermediate of formula 4 with sodium 3-chloro-2-hydroxypropanesulfonate under conditions effective to form the compound of formula 1.

2. The method according to claim 1, wherein the enzyme is a lipase selected from Pseudomonas sp. or Candida antarctica.

3. The method according to claim 2, wherein the lipase is immobilized on a carrier selected from the group consisting of ceramics, diatomaceous earth, acrylic resin and porous fluorine-containing polymer.

4. The process according to any one of claims 1 to 3, further comprising removing water or alcohol by-product from the reaction mixture during step (a).

5. The process according to claim 1, wherein step (b) is carried out in the presence of a base selected from the group consisting of metal hydroxides, metal carbonates and metal bicarbonates.

6. The process according to claim 1, wherein step (b) is carried out in the presence of a solvent selected from the group consisting of water, C2-C5 alcohols, ether-alcohols and mixtures thereof.

7. The method according to claim 1, comprising: (a) contacting a mixture comprising at least two acids or esters of Formula 2 with a dialkylamino-alcohol of Formula 3 in the presence of an enzyme under conditions effective to form at least two intermediates of Formula 4, wherein the at least two acids or esters of Formula 2 have different R substituents, and the at least two intermediates of Formula 4 have different R substituents; and (b) contacting the intermediate of Formula 4 with sodium 3-chloro-2-hydroxypropanesulfonate under conditions effective to form a mixture of at least two compounds of Formula 1, The at least two compounds of Formula 1 have different R substituents.

8. The method according to claim 1, wherein RCO- is capryl, capryl or a C6 to C6 fatty acid derived from coconut oil, hydrogenated coconut oil, hydrogenated and / or fractionated coconut fatty acids, palm kernel oil, hydrogenated palm kernel oil or hydrogenated and / or fractionated palm kernel fatty acids. 20 acyl group; R 1 is 1,3-butylene; R 2 and R 3 is methyl; and R 4 It is 2-hydroxy-1,3-propylene.

9. A method for preparing a compound having formula 1: in R is selected from C5-C 19 Alkyl, C5-C 17 Alkenyl and C5-C 17 Dienyl; R 1 and R 2 With N + Connected to form a heterocyclic ring, the heterocyclic ring is piperidinium; R 1 is C1-C8 alkylene; R 2 and R 3 are each independently selected from C1-C6 alkyl and C1-C6 alkenyl; and R 4 is 2-hydroxy-1,3-propylene, The method comprises: (a) contacting an acid or ester of Formula 2 with a dialkylamino alcohol of Formula 3 in the presence of an enzyme under conditions effective to form an intermediate of Formula 4: Among them, R 1 , R 2 and R 3 As defined above, R 7 is hydrogen or C1-C6 alkyl; and (b) contacting the intermediate of formula 4 with sodium 3-chloro-2-hydroxypropanesulfonate under conditions effective to form the compound of formula 1.

10. The method of claim 9, wherein the enzyme is a lipase selected from Pseudomonas sp. or Candida antarctica.

11. The method according to claim 10, wherein the lipase is immobilized on a carrier selected from the group consisting of ceramics, diatomaceous earth, acrylic resin and porous fluorine-containing polymer.

12. The process of any one of claims 9-11, further comprising removing water or alcohol by-product from the reaction mixture during step (a).

13. The process according to claim 9, wherein step (b) is carried out in the presence of a base selected from the group consisting of metal hydroxides, metal carbonates and metal bicarbonates.

14. The process according to claim 9, wherein step (b) is carried out in the presence of a solvent selected from the group consisting of water, C2-C5 alcohols, ether-alcohols and mixtures thereof.

15. The method according to claim 9, comprising: (a) contacting a mixture comprising at least two acids or esters of Formula 2 with a dialkylamino-alcohol of Formula 3 in the presence of an enzyme under conditions effective to form at least two intermediates of Formula 4, wherein the at least two acids or esters of Formula 2 have different R substituents, and the at least two intermediates of Formula 4 have different R substituents; and (b) contacting the intermediate of Formula 4 with sodium 3-chloro-2-hydroxypropanesulfonate under conditions effective to form a mixture of at least two compounds of Formula 1, The at least two compounds of Formula 1 have different R substituents.

16. The method according to claim 9, wherein RCO- is capryl, capryl or a C6 to C6 fatty acid derived from coconut oil, hydrogenated coconut oil, hydrogenated and / or fractionated coconut fatty acids, palm kernel oil, hydrogenated palm kernel oil or hydrogenated and / or fractionated palm kernel fatty acids. 20 acyl group; R 1 and R 2 With N + Connecting to form 3-piperidinium, 4-piperidinium, 3-piperidiniummethyl or 4-piperidiniummethyl; R 3 is methyl; and R 4 It is 2-hydroxy-1,3-propylene.

Images