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EP0719249A1 - Herstellung von amidosäuren aus carbonsäureestern und aminosäuresalzen - Google Patents

Herstellung von amidosäuren aus carbonsäureestern und aminosäuresalzen

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Publication number
EP0719249A1
EP0719249A1 EP94929159A EP94929159A EP0719249A1 EP 0719249 A1 EP0719249 A1 EP 0719249A1 EP 94929159 A EP94929159 A EP 94929159A EP 94929159 A EP94929159 A EP 94929159A EP 0719249 A1 EP0719249 A1 EP 0719249A1
Authority
EP
European Patent Office
Prior art keywords
acid
amido
formula
amido acid
phenyl ester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP94929159A
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English (en)
French (fr)
Inventor
Stephen Wayne Heinzman
Jeffrey Scott Dupont
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Procter and Gamble Co
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Procter and Gamble Co
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Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0719249A1 publication Critical patent/EP0719249A1/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to the chemical synthesis of amido acids, and their conversion to amido acid phenyl ester sulfonates for use as bleach activators
  • This conversion can be direct by reaction of the amido acids with phenol sulfonic acid derivatives; or by the conversion of the amido acids to their phenyl ester form and then the conversion of said amido phenyl esters into their sulfonated form, or by the conversion of the amido acids to their anhydride and then reaction with sodium phenol sulfonate to form the amido acid phenyl ester sulfonates
  • the amido acids comprise one class of chemicals whose amido and carboxylate functional groups suggest their use as surfactants (i.e., sarcosinates), fabric softeners, antistatic agents and the like.
  • the amido acids constitute a basic raw material for the amido phenyl ester sulfonate class of chemicals which can serve as bleach activators in laundry detergents and other types of bleach-containing cleaning compositions.
  • Such activators have several desirable attributes such as excellent bleaching performance with minimal color damage on fabric dyes, good washing machine compatibility and a good odor profile in the wash.
  • the amido acids and their aforementioned derivatives are potentially obtainable from inexpensive raw materials.
  • amido acids Unfortunately, the synthesis of certain amido acids is somewhat complicated and can involve the use of solvents, with additional problems associated with recycle streams and the like. Problems can also arise with the formation of undesirable colored by-products. Moreover, the conversion of the amido acids to their phenyl ester sulfonate form is not straightforward and can be surprisingly problematic.
  • the present invention provides a simple method for the synthesis of amido acids. It also provides four methods for converting amido acids into amido acid phenyl ester sulfonates which are suitable for use as bleach activators in laundry detergents, and the like.
  • the first method is a simple, one-step esterification of amido acid with phenol to provide an amido acid phenyl ester which can subsequently be reacted with SO 3 and neutralized in conventional fashion to give amido acid phenyl ester sulfonates.
  • the second prepares the amido acid phenyl ester by transesterification of ester derivatives of phenol followed by the conversion to the amido acid ester sulfonates as described for the first method.
  • the third method involves transesterification of ester derivatives of phenol sulfonic acid or salt (typically sodium or potassium) with amido acid to provide amido acid phenyl ester sulfonates directly.
  • the fourth method involves making the anhydride of the amido acid and reacting this anhydride with sodium phenolsulfonate to also produce amido acid phenyl ester sulfonates directly.
  • reaction sequences herein proceed in acceptable yields (typically 60%, and higher) and, importantly, result in products with minimal discoloration
  • the reactions may be conducted without added solvents, i.e., the reactants act as solvents.
  • the reaction products need not be extensively purified which further improves the overall economics of the processes.
  • the present invention encompasses a method for preparing amido acids and salts thereof of the formulae
  • R and R 2 are independently a C 1 or higher hydrocarbyl substituents, R 1 isC 1 -C 1 0 hydrocarbylene substituent, and M is a cationic moiety selected from alkali metal salts and hydrogen, by the steps of
  • R, R 1 , and R 2 are as described before, and M is an alkali metal salt
  • step (b) optionally, neutralizing the amido acid salt formed by step (a) to form the amido acid, whereby M is hydrogen in formulae IA and IB
  • the preferred method for preparing said amido acids is conducted at a temperature from about 80°C to about 200°C, especially from about 120°C to about 180°C
  • the method herein employs an amino acid salt selected from the salts of 6-aminocaproic acid, sarcosine, glycine, taurine, N-methyl taurine, serine, isoserine, methionine, and proline
  • reaction In order to facilitate mixing of the reactants and minimize reaction time, it is preferred to conduct the reaction in an alcohol solvent which has a boiling point of at least 100°C
  • a basic catalyst such as sodium methoxide also accelerates the reaction
  • the reaction proceeds in greater than 90% gagd with a molar ratio of fatty methyl ester reactant to amino acid salt reactant to basic catalyst of about 1:1:0.2.
  • the invention also encompasses a method for preparing amido acid phenyl esters of the formula wherein R, R 1 and R 2 are as described herein before,
  • the strong acid (non-boric acid) catalyst is a member selected from the group consisting of sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, toluenesulfonic acid, phosphonic acid and mixtures thereof.
  • the mole ratio of boric acid to the strong acid catalyst is at least about 1 : 1, more preferably at least about 1 :3.6.
  • the mole ratio of amido acid to strong acid catalyst is at least about 1 :0.05 and more preferably about 1 :0.25.
  • This esterification reaction is preferably conducted at a temperature in the range from about 180°C to about 210°C, and is most preferably conducted without added solvent.
  • the esterification herein is preferably conducted at a temperature of about 180-190°C in the absence of solvent, with 98% sulfuric acid as the acidic catalyst, and at a mole ratio of boric acid to sulfuric acid of at least about 1 :3.6.
  • an excess of phenol is used, typically a phenol:amido acid mole ratio of about 5: 1 to about 20:1.
  • the invention also encompasses a method for preparing amido acid phenyl esters of the Formula (II) comprising reacting an amido acid having Formula (IA) above with a phenyl ester of a lower molecular weight carboxylic acid moiety, preferably phenyl acetate, in the presence of a basic catalyst.
  • the basic catalyst can be selected from the group consisting of carboxylate salts, carbonates, imidazole and mixtures thereof.
  • the mole ratio of basic catalyst to amido acid is at least about 0.001 : 1, more preferably at least about 0.01 : 1.
  • the mole ratio of amido acid to phenyl ester is at least about 1 : 1 and more preferably about 3: 1.
  • This transesterification reaction is preferably conducted at a temperature in the range from about 160°C to about 210°C, and is most preferably conducted without added solvent.
  • the invention herein also provides a method for preparing bleach activators comprising sulfonating and neutralizing an amido acid phenyl ester of Formula (II) prepared according to the foregoing processes to produce amido acid phenyl ester sulfonates of the formula: wherein R, R 1 and R 2 are as described hereinbefore, the amido acid phenyl ester sulfonate is predominantly para-substituted (as pictured) although ortho-substitution is acceptable, and M is a cationic moiety, preferably a mono- or divalent metal salt (e.g., potassium, sodium) or hydrogen, which for use of these compounds as bleach activators should be sutstantially free of transition metal ions (known to cause instability of peroxy compounds).
  • R, R 1 and R 2 are as described hereinbefore
  • M is a cationic moiety, preferably a mono- or divalent metal salt (e.g., potassium, sodium) or hydrogen, which for use of these compounds as bleach
  • the invention also encompasses a method for preparing amido acid phenyl ester sulfonates of the Formula (III) above by reacting an amido acid of Formula (I A) above with an ester derivative of phenol sulfonic acid or salt of the formula.
  • M is a cationic moiety as described herein before, and R 3 is an acid moiety, preferably a lower (C 2 -C 5 ) molecular weight carboxylic acid moiety such as the most preferred acetic acid moiety.
  • R 3 is an acid moiety, preferably a lower (C 2 -C 5 ) molecular weight carboxylic acid moiety such as the most preferred acetic acid moiety.
  • Reaction temperatures for this transesterification reaction are at least about 150°C, preferably from about 180°C to about 220°C, for reactions with acetoxy benzene sulfonic acid sodium salt. Lower reaction temperatures, from about 140°C to about 180°C, are preferred for reactions with acetoxy benzene sulfonic acid.
  • the invention also provides a method for preparing amido acid phenyl ester sulfonates of the Formula (III) above by reacting an amido acid of Formula (IA) above with a lower (C 4 -C 10 ) molecular weight carboxylic acid anhydride (e.g., (R 4 CO) 2 O, wherein each R 4 is the same or different C 1 -C 4 hydrocarbyl substituents), preferably acetic anhydride, to form the amido acid anhydride.
  • the amido acid anhydride is then reacted with phenolsulfonate salt (preferably the sodium salt) to form the desired amido acid phenyl ester sulfonates.
  • the amido acid anhydride is prepared by reacting amido acid with the lower molecular weight carboxylic acid anhydride in a molar ratio ranging from about 1 :3 to about 5: 1. Reaction temperatures are from about 70- 1 10°C with reaction times of about 1-18 hr. Catalysts such as sodium acetate, sodium carbonate, sodium bicarbonate, imidazole, or methanesulfonic acid can be used. At the end of the reaction, carboxylic acid and/or excess carboxylic acid anhydride, such as acetic acid and/or excess acetic anhydride, are removed by distillation
  • the crude amido acid anhydride mixture is then reacted with anhydrous sodium phenolsulfonate in a molar ratio of about 1 : 1. Reaction temperatures are from about 100-200°C with reaction times of about 1-6 hr. Basic catalysts such as sodium acetate or imidazole can be used. If the crude amido acid anhydride contains excess amido acid, then solvent is not needed. If excess amido acid is not present in the amido acid anhydride, solvents such as dimethylformamide, toluene, or xylenes can be used.
  • sequence ( 1 ) for the synthesis of the amido acids and reaction sequence (2a) and (2b) for their conversion to the phenyl ester form are shown below.
  • Sequence (3) illustrates the conventional sulfonation step, which typically includes base neutralization to prepare the salt form of the amido phenyl ester sulfonate class of bleach activators.
  • Sequences (4a), (4b), and 5 show alternative methods for preparing the amido phenyl ester sulfonate directly from the amido acid prepared by Sequence (1).
  • the reaction sequences as illustrated employ octanoic acid methyl ester and 6-aminocaproic acid sodium salt, but this is only by way of illustration and not limitation, as will be seen hereinafter.
  • the carboxylic acid ester reactant can be selected from alkyl esters (preferably methyl or ethyl) of straight chain aliphatic, branched chain aliphatic, saturated or unsaturated, aromatic, heroaromatic, ethercarboxylic and cycloaliphatic carboxylic acids.
  • alkyl esters preferably methyl or ethyl
  • Nonlimiting examples include methyl or ethyl esters of the following carboxylic acids: acetic, propionic, butyric, caprylic, caproic, nonanoic. 3,5,5-trimethylhexanoic, decanoic, lauric, myristic, palmitic, stearic. oleic, linoleic.
  • the amino acid salt reactant in Sequence 1 can be, for example: the sodium salts of amino acids derived from hydrolysis of 5-12 membered ring lactams such as 5-aminovaleric acid and 6-aminocaproic acid or sodium salts of sarcosine. glycine. taurine, N-methyl taurine, serine. isoserine. methionine. and proline. and mixtures thereof
  • the sodium salts of the amino acids can be generated either by neutralizing the amino acids with a sodium hydroxide solution and then drying or by neutralizing with sodium methoxide (convenient for lab preparations since it does not introduce water).
  • Lactam hydrolysis is necessary if a lactam is used as the source of the ammo acid salt reactant.
  • An alcohol solvent is used in which dry sodium hydroxide has at least partial solubility. In order to complete the hydrolysis in a 2-8 hr reaction time, the alcohol used must have a boiling point above 100°C. The alcohol will also serve as the solvent for the amide formation step It is preferred that the alcohol boiling point be less than 200°C, since it must be removed from the amido acid prior to Sequence 2 or 4 and for economical reasons be easily recycled.
  • 1-Butanol is an especially preferred solvent.
  • Lactam hydrolysis requires a molar ratio of sodium hydroxide to lactam of at least 1 1 , preferably 1 05 1
  • the sodium methoxide catalyst to be used in the amide formation step may be added during lactam hydrolysis, since alcohol solution or suspension of amino acid salt reactant is used directly in the amide formation step
  • the hydrolysis proceeds most readily when the amount of solvent used is the minimum necessary to dissolve the sodium hydroxide.
  • Amidation requires that the amino acid salt reactant be at least partially miscible in the carboxylic acid ester
  • a solvent is necessary to achieve partial miscibility
  • no solvent is necessary if the reaction is performed at 180-200°C.
  • Reaction temperatures in the amidation step will typically be above about 80°C and below about 200°C and are preferably in the range from about 1 10°C to about 180°C
  • Reaction times can vary, of course, depending on the reactant volumes being employed. However, as a general rule for reactions in the 100 mls size range, a reaction time in the range from about 0 5 hours to about 4 hours is sufficient
  • the alcohol originating from the carboxylic acid ester typically methanol
  • the alcohol solvent typically butanol
  • Reaction stoichiometry in the amidation step employs a molar ratio of amino acid salt reactant to carboxylic acid ester to basic catalyst of about 1 1.05 0 2
  • the basic catalyst is preferably sodium methoxide
  • amido acid salt After the amidation step, to form the amido acid the amido acid salt must be neutralized to the amido acid and the alcohol solvent removed
  • acids sulfuric, formic acids
  • acetic acid is not as preferred as formic acid because sodium acetate is more soluble than sodium formate in methanol/butanol
  • acetic acid is convenient if 1-butanol is the reaction solvent Sodium formate is sparingly soluble in 1-butanol and precipitates.
  • Amido acid is soluble in the butanol Typically a molar ratio of acid to amido acid salt of about 1.1 is used
  • butanol is removed from the amido acid by distillation and can be recycled.
  • Sequence 2a The preparation of the phenyl esters of carboxylic acids, especially the amido acids, is as follows.
  • Useful carboxylic acid reactants in Sequence 2 include all of the amido acids prepared per Sequence 1.
  • the phenol reactant includes phenol, itself, as well as alkyl substituted phenols such as cresols and phenol derivatives such as phenolsulfonates
  • the strong acid catalyst used in Sequence 2 can be any of the strong protonic acid catalysts used in Sequence 1 Sulfuric acid (98%) is convenient, inexpensive and preferred. Under the process conditions the sulfuric acid sulfates the phenol in situ. so that the strong acid catalyst is at least partially the phenolsulfonic acid
  • ester formation involves the formation of a triphenol borate ester by a reaction of a borate material with the phenolic material, followed by exchange of phenol for carboxylic acid to form a carboxylic/boric anhydride species, followed by some manner of phenol displacement of the borate ester from the carboxylic-boric anhydride species; followed by exchange of water to form the borate species and reform the triphenol borate active catalyst agent.
  • any borate or boric acid material, or precursor thereof, which results in the formation of a triphenol borate ester with phenol or substituted phenols can be used herein Typical examples of such materials include boric acid, boric acid precursors, boric acid esters, for example, materials such as borax, tributylborate, triphenylborate, and the like.
  • boric acid is a convenient and inexpensive catalyst for use in Sequence 2.
  • Sequence 2 any air in the system causes a drastic darkening of the reaction mixture, just as in Sequence 1. Consequently, nitrogen sparging or sparging with another inert gas in order to provide a nonoxidizing condition is preferably used.
  • an inert reaction vessel such as those made from glass, quartz, stainless steel, or the like.
  • Reaction temperatures of at least 150°C, preferably from about 180°C to about 200°C, are preferred, and reaction times are similar to those disclosed for Sequence 1, typically 2 to 4 hours.
  • Water (which may be present in the starting materials) is removed during the first 30 minutes of the reaction by azeotropic distillation of phenol/water. The presence of water is detrimental to the overall yield because it can result in the hydrolysis of the amide linkage of the amido acids and/or amido acid phenol esters.
  • the strong acid catalyst proportion is at least about 0.01 mole, preferably from about 0.25 mole to about 0.5 mole.
  • the boric acid is used at levels from about 0.01 mole to about 0.07 moles, based on the amido acid reactant.
  • reaction product consists of the desired amido acid phenol ester. carboxylic acid phenyl ester and unreacted amido acid. This reaction product can be purified prior to sulfonation, or can be sulfonated without further purification since the contaminants are compatable with many detergent compositions.
  • Sequence 2b Transesterification of a phenyl ester of a lower (C 2 -C 5 ) molecular weight carboxylic acid moiety, preferably phenyl acetate, with amido acid in the presence of a basic catalyst provides amido acid phenyl ester in good yield
  • the basic catalyst can be selected from the group consisting of carboxylate salts, carbonates, imidazole and mixtures thereof
  • the mole ratio of basic catalyst to amido acid is at least about 0.01 : 1 , more preferably at least about 0.01 : 1
  • the mole ratio of amido acid to phenyl ester is at least about 1: 1 and more preferably about 3: 1
  • This transesterification reaction is preferably conducted at a temperature in the range from about 160°C to about 210°C, and is most preferabh conducted without added solvent
  • Sequence 3 Sulfonation of the amido acid phenol ester can be conducted using sulfur trioxide, sulfur trioxide vapor, chlorosulfonic acid, sulfur t ⁇ oxide complexes, oleum, sulfamic acid, and the like, plus other typical sulfonating agents Reaction can be carried out without solvent, or, if desired, can be conducted in solvents such as sulfur dioxide, methylene chloride, ethylene dichloride, carbon tetrachloride, fluorotrichloromethane, and the like. It is preferred to run the sulfonation reaction of Sequence 3 without solvent Of course, unsaturated materials should be avoided in the reaction mixture, primarily due to color formation
  • the sulfonation reaction of Sequence 3 is highly acidic and inert reaction vessels are again used
  • Reactors can be of the continuous film or continuous cascade types, for example
  • sulfur trioxide is used as the sulfonating reactant
  • it is preferably introduced in an inert gas stream (nitrogen or dry air) containing 1-20% by weight sulfur trioxide Reaction temperatures are typically 20°C to 200°C with reaction times of from 5 to 180 minutes (based on 1 mole of amido acid phenyl ester being sulfonated)
  • the amido acid phenyl ester is present at a 1 mole level and this sulfonating agent used at a 0.9- 1 .5 mole level
  • Product work-up involves neutralizing the crude reaction mixture to pH 4-6 with base such as sodium bicarbonate, sodium acetate, sodium formate, or the like
  • Sequence 4 Amido acid phenyl ester sulfonate can also be made by transesterification of acetoxybenzenesulfonic acid or its salt (typically sodium or potassium) with amido acid. If acetoxybenzenesulfonic acid sodium salt is used, then a 3-4 mol equivalent excess of amido acid is necessary to act as solvent If acetoxybenzenesulfonic acid is used, then a 1.2 mol equivalent excess of amido acid is sufficient Either base or acid catalysis promotes the transesterification of acetoxybenzenesulfonic acid sodium salt, sodium acetate or sulfuric acid are typically used Transesterification with acetoxybenzenesulfonic acid does not require a catalyst A stream of inert gas is passed over the reaction so as remove acetic acid as it is formed and provide a nonoxidizing environment As in Sequence 3. inert reaction vessels are preferred
  • Acetoxybenzenesulfonic acid sodium salt can be prepared from reaction of excess acetic anhydride with dry phenolsulfonic acid sidium salt
  • Acetic anhydride or acetic acid can serve as a solvent
  • Acetoxybenzenesulfonic acid can be made from reaction of acetic anhydride with dry phenolsulfonic acid Alternatively, it can be made from sulfonation of phenyl acetate with sulfur trioxide or chlorosulfonic acid
  • Sequence 5 Formation of the amido acid anhydride is accomplished by reacting amido acid with acetic anhydride. Reaction temperatures between 70 and 120°C are favored to avoid acylation of the amide nitrogen
  • the molar ratio of amido acid to acetic anhydride is from 1: 3 to 5: 1 If the molar ratio is 3: 1 and higher, it is not necessary to add a solvent for the reaction with sodium phenolsulfonate
  • acetic acid and/or acetic anhydride are distilled from the reaction mixture to give the crude amido acid anhydride
  • Sodium phenolsulfonate is then added in a 1 1 molar ratio to the amido acid anhydride and the reaction is heated at from 100 - 200°C for 1-18 hr
  • Toluene or xylenes can be used as solvents for this reaction
  • unreacted amido acid can be removed from the amido acid phenyl ester sulfonate by washing with
  • amido acids ie sarcosinate surfactants
  • fatty acid chlorides ie sarcosinate surfactants
  • amino acid chlorides amino acid chlorides
  • sodium chloride waste is generated, which is not a factor in the present invention.
  • the process does not involve large amounts of water, which would have to be removed prior to Sequence 2
  • esterification of the amido acid can be achieved by forming the acid chloride of the amido acid and subsequently reacting it with phenol or phenolsulfonate
  • the prior art reaction has the same problems as those mentioned above for the amido acid synthesis. While esterification of conventional carboxylic acids with phenols using boric/sulfuric acid has been described in the Lowrance article, cited hereinabove, the reaction conditions described by Lowrance fail to esterify amido acids in any reasonable yields. For example, the present process employs much higher reaction temperatures than those disclosed by Lowrance, said temperatures being achieved by using phenol as the azeotroping agent. Moreover, much higher amounts of sulfuric acid catalyst are used herein, which promotes the desired reaction while reducing side reactions.
  • Sequences 1, 2a, and 3, Sequences 1, 2b, and 3, Sequences 1 and 4, or Sequences 1 and 5 have several advantages, including one or more of: low cost starting materials; minimum number of reaction steps; good yields for each step; reasonable reaction times; no waste by-products; ability to recycle starting materials; and no solids handling until the last step.
  • This method is applicable to the determination of the relative content of octanoic acid, decanoic acid, octanoic acid phenyl ester, octanoyl caprolactam, 2-pyrrolidinone, octanoyl diamido acid, phenylesters of C 8 -C 1 0 amidocaproic acid, C 8 amidobutyric acid, caprolactam, 6-aminocaproic acid. C 8- C 10 amidocaproic acid, and phenol, in reaction samples.
  • the components listed above are separated, after silylation, by temperature programmed GC on a 15m DB 1 column.
  • a hot (300°C) split injector is used and detection is by FID.
  • GC area % is used to estimate content of components in a sample.
  • the materials containing active hydrogens are derivatized with BSTFA containing 1% TMCS.
  • Octanoyl amidobutyric acid 17.3 g) Inlet oven tracking Off Octanoyl caprolactam 19 5 (239) * h) FID detector 330°C Octanoyl amidocaproic acid 23.2. 24 ⁇ temperature (329) * i) Oven initial 50°C Decanoyl amidocaproic 25.3. 26.2 temperature acid
  • Step A Hydrolysis of Caprolactam -
  • a three-neck, 2 L round bottom flask is fitted with mechanical stirrer and condenser and heated with an oil bath. Throughout all reactions, stirring and a static pressure of nitrogen is maintained.
  • Sodium hydroxide pellets 98.5% (34.76 g, 0.856 mol), 25% sodium methoxide in methanol (33.7 g, 0.156 mol), methanol (100 mL), and 1-butanol (210 mL) are added to the flask. The mixture is heated to reflux for about 20 min to dissolve the sodium hydroxide and then concentrated by distilling away 130 mL of solvent.
  • Caprolactam 99% (88.06 g, 0.78 mol) is added and the mixture refluxed for 3.5 hr. After 15 min, the mixture becomes cloudy and foamy. After 1.5 hr, the reaction is clear. After 2.5 hr, the reaction becomes solid. After 3.5 hr, 1-butanol (60 mL) is added to solubilize the reaction mixture. HNMR and TLC indicate >90% yield of 6-aminocaproic acid sodium salt.
  • Step B Amidation of fatty methyl ester -
  • the clear solution of 6- aminocaproic acid sodium salt from Step A is allowed to cool until it starts to solidify and then methyl caprylate 99% (130.91 g , 0.819 mol) is added.
  • the mixture is heated to reflux and it becomes clear after 2 min. After 9 min. the reaction mixture becomes solid.
  • the reaction is kept at reflux for a total of 1 hr
  • methanol (250 mL) / 1-butanol (500 mL) is added and the reaction mixture refluxed until most of the solid is dispersed (about 10 min).
  • HNMR and TLC indicate ⁇ 90% yield of amido acid salt.
  • Step C Neutralization of amido acid sodium salt - Formic acid 96% (50.35 g, 1.05 mol) is added to the slightly cooled dispersion of amido acid sodium salt from above. The mixture is refluxed for about 10 min until only a fine white precipitate (sodium formate) remains. The reaction mixture is allowed to cool to room temperature and then suction filtered to remove sodium formate. The sodium formate precipitate is washed with 1-butanol (200 mL). HNMR indicates that the sodium formate contains a trace of amido acid. Butanol and methanol are removed from the amido acid by vacuum distillation to give C8 amidocaproic acid ( 172 4 g, 77% yield based on caprolactam).
  • reaction is refluxed 15 min to neutralize the taurine and then methanol is distilled off using the Dean-Stark trap
  • the reaction mixture is then heated to 160°C and methyl myristate (24.7 g, 0.10 mol) is added Reaction is kept at 160°C for 1.0 hr during which methanol (7 mL) is collected in the Dean-Stark trap.
  • the reaction is allowed to cool, acetone (300 mL) is added, and the mixture cooled to 10°C.
  • the precipitate is collected by filtration, washed with cold acetone (200 mL), and dried in oven at 60°C to give the desired product as a white solid (33.0 g).
  • reaction is kept at 200° C for 4 hours using a high temperature oil bath, continuously purging with nitrogen During the first hour, of reaction time, 50 mL of phenol is removed via the Dean-Stark trap. After 4 hours reaction time, the reaction mixture is analyzed by GC to determine % conversion of C8 amidocaproic acid to C8 amidocaproic acid phenyl ester (see Table 5). Reaction mixture is brown after 4 hours. Phenol is removed by vacuum distillation (90-100°C, 4.3 mm) to give the desired C8 amido acid phenyl ester as a brown solution (31.6 g) with the analysis shown in Table 7.
  • Amidocaproic acid phenyl ester (22.00 g, 0.0634 mol) is placed in 100 mL 2-neck round-bottom fitted with a glass tube reaching the bottom of the flask and a condenser connected to a bubbler.
  • the flask is heated to 50°C in an oil bath to melt the phenyl ester.
  • Sulfur trioxide (5.0 g, 2.6 mL, 0.0634 mol) vapor diluted with nitrogen is added to the reaction over 1 hour through the glass tube.
  • the glass tube is connected via Teflon tubing to another flask heated at 65°C in which liquid sulfur trioxide is placed.
  • Nitrogen is bubbled through the liquid sulfur trioxide to obtain the gas mixture.]
  • the reaction is then heated at 50°C for an additional 30 minutes after the sulfur trioxide addition.
  • the reaction is allowed to cool to room temperature and then poured into saturated aqueous sodium bicarbonate.
  • the product precipitated as a white solid and is collected by vacuum filtration. After drying, the product ( 17.7 g) is obtained in 65% yield.
  • reaction mixture is recrystallized from methanol (370 mL) to obtain a first crop (15.1 g) and a second crop (4 7 g) of desired product (75% recrystallized yield based on sodium acetoxybenzenesulfonate)
  • the reaction mixture is heated at 1 10°C for 3 hr with a nitrogen sparge; 10 mL of distillate is collected in the Dean-Stark trap Then acetic acid and excess acetic anhydride is removed by vacuum distillation to obtain amido acid anhydride.
  • the crude amido acid anhydride is dispersed in ether (60 mL), filtered, and dried to obtain nearly pure amido acid anhydride (indicated bv HNMR) as a white solid (8.6 g).
  • ether 60 mL
  • filtered filtered, and dried to obtain nearly pure amido acid anhydride (indicated bv HNMR) as a white solid (8.6 g).
  • a mild lubricious soap bar composition is prepared in conventional extrusion apparatus, as follows. The bar resists dry cracking and wet smear.
  • a laundry bleaching system suitable for use alone or in admixture with a conventional granular laundry detergent is as follows.
  • composition can be added to water at levels of 100 ppm, and above, to provide a fabric bleaching action. What is Claimed is:
  • R and R 2 are independently a C 1 or higher hydrocarbyl substituents, R 1 is C 1 -C- 1 0 hydrocarbylene substituent, and M is a cationic moiety selected from alkali metal salts and hydrogen, by the steps of:
  • R, R 1 and R 2 are as described before, and M is an alkali metal salt
  • step (b) optionally, neutralizing the amido acid salt formed by step (a) to form the amido acid, whereby M is hydrogen in formulae IA and IB.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Detergent Compositions (AREA)
EP94929159A 1993-09-14 1994-09-13 Herstellung von amidosäuren aus carbonsäureestern und aminosäuresalzen Withdrawn EP0719249A1 (de)

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US12100793A 1993-09-14 1993-09-14
US121007 1993-09-14
PCT/US1994/010138 WO1995007882A1 (en) 1993-09-14 1994-09-13 Synthesis of amido acids from carboxylic acid esters and amino acid salts

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EP0884306A2 (de) * 1993-09-14 1998-12-16 The Procter & Gamble Company Herstellung von Amidosäuren aus Carbonsäuren und Lactamen

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US5466840A (en) * 1994-08-22 1995-11-14 Eastman Chemical Company Process for preparing purified alkali metal salts of 4-sulfophenyl-[(1-oxyalkanoyl)amino]alkanoate without isolation of intermediates
US5840469A (en) * 1997-05-13 1998-11-24 Imation Corp. Gallic acid as a laser direct thermal developer
DE19956862A1 (de) 1999-11-25 2001-06-21 Axiva Gmbh Verfahren zur Gewinnung und Reinigung substituierter Benzolsulfonate
DE19956863A1 (de) * 1999-11-25 2001-06-21 Axiva Gmbh Verfahren zur Isolierung von Amidosäurephenylestersulfonaten aus Wasser-Lösungsmittel-Gemischen
US6660712B2 (en) 2000-06-02 2003-12-09 Dale Elbert Van Sickle Stabilization of amido acids with antioxidants
US8822711B2 (en) * 2011-07-28 2014-09-02 Conopco, Inc. Method for preparing fatty acyl amido carboxylic acid based surfactants
US8853433B2 (en) * 2011-07-28 2014-10-07 Conopco, Inc. General method for preparing fatty acyl amido based surfactants
BR102013031932A2 (pt) * 2012-12-13 2014-10-14 Dow Agrosciences Llc Processos melhorados para o isolamento do ácido 4-amino-3-cloro -6-(4-cloro-2-fluoro-3-metoxifenil)-piridina-2-carboxí lico
CN105531256B (zh) * 2013-08-19 2017-11-07 斯泰潘公司 用于制备n‑酰基氨基酸盐的方法
CN109761836B (zh) * 2019-02-21 2020-05-15 中南大学 酰胺类化合物的制备方法
CN114181118B (zh) * 2021-11-25 2022-10-14 张家港格瑞特化学有限公司 一种脂肪酰基牛磺酸盐的合成工艺
CN114276270A (zh) * 2021-12-10 2022-04-05 湖北文理学院 一种具有酰胺键的化合物的合成方法
US20240209282A1 (en) * 2022-12-07 2024-06-27 The Procter & Gamble Company N-acyl aminoalkane sulfonate surfactants and derivatives thereof

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CA2170487A1 (en) 1995-03-23
WO1995007882A1 (en) 1995-03-23
JPH09502720A (ja) 1997-03-18

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