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    • 专利摘要:
    abstract method for producing n-acyl amino acid surfactants using n-acyl amino acid surfactants or the corresponding anhydrides as catalysts a process for producing surfactants based on n-acyl amino acids of formula i, formula i in which, r is selected from alkyl group c6 to c22, r1 is selected from h, alkyl c1 to c4, r2 is selected from all the carbon a groups of natural amino acids, r3 is selected from coox, ch2-so3x, x is selected from li +, na + or k + ; said process comprising the steps of a) the preparation of fatty acid chlorides by the halogenation of fatty acids, both with phosgene and with thionyl chloride, in the presence of a catalytic amount of the same or other n-acyl amino acid surfactant of formula i , or anhydrides of the same surfactant, formula ii, formula ii where, r = c6 to c22 alkyl group, r1 = h, c1 to c4 alkyl, r2 = all carbon a groups of natural amino acids, n = 0 to 4, x = c, so and b) the reaction of fatty acid chloride from step (a) with an amino acid, in the presence of a base, under typical aqueous conditions of schotten baumann, so that said process does not employ a purification step.
    公开号:BR112015003383B1
    申请号:R112015003383
    申请日:2012-09-28
    公开日:2020-02-04
    发明作者:Kishor Desai Archana；Jagannath SAWANT Bhagyesh；Bhikaji Parab Bharat；Keshwar BARAI Kamlesh；Koshti Nirmal；Mandar KATDARE Pradnya；Subhash Powale Rajendra；Vishnu KADAM Santosh；Uppalaswamy Pilli Srinivas
    申请人:Galaxy Surfactants Ltd；
    IPC主号:
    专利说明:

    METHOD TO PRODUCE N-ACYL AMINO ACIDS SURFACTANTS USING N-ACYL AMINO ACID SURFACTANTS OR ANYRIDED CORRESPONDENTS AS CATALYSTS
    Invention Title [001] Method for producing N-acyl amino acid surfactants using N-acyl amino acid surfactants or the corresponding anhydrides as catalysts.
    Field of the invention [002] The present invention relates to a two-step, cost-effective process for the manufacture of surfactants based on amino acids, using said surfactants as catalysts for the synthesis of the high quality intermediate and with a quantitative yield. More particularly, the present invention relates to a process for the preparation of N-acyl amino acid surfactants, by catalyzing the synthesis of fatty acid chloride by the same N-acyl amino acid surfactants that are to be manufactured.
    Knowledge and state of the art of the invention [003] A-acyl amino acid surfactants are widely used in personal care applications, in addition to other industrial applications. These surfactants are included in the category of anionic surfactants and are significantly milder than other anionic surfactants. For example, surfactants such as sodium lauroyl sarcosinate, sodium myristoyl sarcosinate, sodium cocoyl glycinate and sodium cocoyl Nmethyl taurate are commercially used to wash the face, wash the body, as they have good cleaning characteristics and are milder for skin and hair, compared to other anionic surfactants. The alcoholic sarcosinates are applied in mouthwashes and dentifrices in general, due to their bacteriostatic activity. There are a number of other areas where N-acyl amino acids are commercially used, such as in petroleum derivatives, as lubricants, in metal processing and ore flotation. (N-acyl amino acid as surfactants, JD Spivack, Chapter 16, in anionic surfactants, Vol. 7, Surfactant Science Series, edited by WM Linfield). Commercially, surfactants are manufactured by means of synthesis in two stages, which involves fatty acid and various amino acids, such as glycine, sarcosine, N-methyl taurine,
    2/28 alanine, aspartic acid, glutamic acid, glutamine and arginine. These are some of the most commonly used amino acids in the production of N-acyl surfactants from amino acids. However, practically all chiral, or racemic, natural or synthetic amino acids can be used in the production of N-acyl surfactants. In addition, the amino acids used in the production of surfactants must not be α-amino acids. Also, the group of acids for these amino acids can be any group of acids other than the carboxylic group. Sulfonic amino acids (for example, N-methyl taurine) are condensed with fatty acid chlorides and to create commercial surfactants such as sodium N-methyl-N-cocoyl taurate. In the production of N-acyl amino acid surfactants, the fatty acid or a mixture of fatty acids is reacted with the amino amino, through the intermediation of the fatty acid chloride, under the typical conditions of Schotten Baumann, as shown in scheme 1 ( United States Patent No. 2,790,7799 (1953), United States Patent No. 2,790,779 (1957), United States Patent No. 3,945,931 (1974)).
    + 1-bN CI-b COOH + NaQH / Schotten Baumann water
    COO Na o
    + NaCI
    Scheme 1 [004] Schotten Baumann condensation between fatty acid chloride and an amino acid is typically done in an aqueous medium; however, the use of mixed solvent systems (solvent and water) is also reported (US patent 6,703,517 (2002), US patent 6,569,829 (1999) and US patent application published under No. 2005 / 0085651 (2004) and WO 2009/065590 (2009)). Some other patents report on the preparation and purification of N-acyl surfactants amino acids, which are essentially done following the same route of condensation of fatty acid chloride with amino acids (Japanese patent No. 2,923,101 (1991), Japanese patent application No. 04-149163 (1990), Japanese patent No. 3362468 (1993)).
    + SOCb
    DMF
    scheme 2
    3/28
    + COCb
    DMF
    HCI scheme 3 [005] The precursors of N-acyl amino acid surfactants, fatty acid chlorides, are industrially produced by the reaction of fatty acids and a halogenating agent, or phosgene or thionyl chloride, as shown in schemes 2 and 3. Chlorination is generally catalyzed by N, N-dimethylformamide (DMF). DMF or similar substitute formamides form a complex (Vilsmeier complex) with
    COCh or SOCI2, which is the real catalytic species (US patents 5430186,
    5623082, 5200560, 5278328 and 5166427) in the chlorination of acids.
    Vilsmeier complex [006] At the end of the reaction, the process that isolates the fatty acid chloride (product) from the catalyst complex has always been a difficult problem to get around. Several attempts have been made, but clean separation of the acid chloride (product) catalyst complex is generally not possible (US patents 5,166,427 (1992),
    5,200,560 (1993), 6770783 (2004) 6727384 (2004) and 5247105 (1993).
    [007] The serious disadvantages and complications resulting from the presence of this dark colored catalyst complex (Vilsmeier complex) in the product are well documented and most attempts have been made to improve the separation phase, which is the separation of the phase of the product phase catalyst complex.
    [008] Thus, the removal of DMF or similar catalytic substances, both in the separation phase as in the fractionation / distillation phase involves further processing and the loss of yield of the product of great value. A large part of the Vilsmeier compounds, thus formed, are separated at the conclusion of the reaction, by means of phases that allow the separation. The chlorinating agent complex, corboxamide, tends to settle as a black / brown tar at the bottom of the reaction vessel. The separation phase is the most experienced method for purifying acid chlorides, as disclosed in the United States patents. 5,166,427 (1992), 5,200,560 (1993), 6,770,783
    4/28 (2004), 6,727,384 (2004) and 5247105 (1993).
    [009] Distillation (fractionation) is another way to isolate the product, but not all acid chlorides are capable of distillation. The catalyst complex (Vilsmeier complex) exists in ionic form and, therefore, it is not easy to eliminate it by distillation / fractionation of acid chloride. The catalyst complex remains in decomposition during the distillation. Second, distillation / fractionation losses (fractions with the formamide catalyst and the residue left after distillation) are inevitable.
    [0010] Another serious concern is the toxicity of these formamides or any other organic molecules similar to DMF. DMF is included in dangerous substances and is reported to have a chronic toxic effect and health risk rating 2. In addition, there are no toxicological data available for the other formamides, the DMF analogues, which are able to act as catalysts, but are expected to have similar or higher toxicity. In addition to the concern for health hazards associated with formamides, DMF analogs have the same difficulty in isolating fatty acid chloride (product) from the reaction mass, when used as catalysts, since they form Vilsmeier complexes. with halogenating agents. Thus, the fatty acid chlorides produced by the halogenation of fatty acids, either with phosgene or with thionyl chloride, using formamides, acetamides, or any other analogs as catalysts, require additional purification steps, such as distillation, separation phases or crystallization, etc., DE 2656126 (1977). These additional steps result in significant loss of performance, higher energy consumption and longer processing cycle time, resulting in lower productivity.
    [0011] Since the production of the main intermediates, the fatty acid chlorides, through current state of the art processes, is costly and inefficient, this aspect affects the quality and cost of products such as N-acyl surfactants amino acids , whose worldwide consumption is estimated at 250 thousand metric tons.
    [0012] Therefore, there is a need to significantly improve the production process, so that one can reduce losses as a result of distillation and avoid any other stage of purification of the intermediate, and reduce the cycle time of the
    5/28 process, providing higher productivity.
    [0013] The present invention relates to the production of surfactants based on amino acids, using said surfactants as catalysts for the synthesis of the high quality intermediate and with a quantitative yield. The global process does not harm the environment (significantly reduces the time of the process, provides low energy consumption, without any waste and generation of effluents (no residue after distillation / fractionation)), and has an excellent cost-benefit ratio (low consumption of energy), is efficient (faster rate of catalysis). In addition, the process described in the present patent application avoids the use of toxic catalysts and is applicable to the entire class of the N-acyl amino acid surfactant family.
    Objects of the invention [0014] An object of the present invention is to circumvent the drawbacks of the state of the art.
    [0015] Another object of the present invention is to provide a process for the production of surfactants based on amino acids, using the same surfactants as catalysts for the synthesis of high quality intermediate and with a quantitative yield.
    [0016] Yet, another object of the present invention is to provide a cost-effective two-step process for the industrial manufacture of the entire class of N-acyl amino acid surfactants.
    Summary of the invention [0017] The present invention relates to a process for producing surfactants based on N-acyl amino acids, of Formula I,
    Formula I in which, R is selected from the C6 to C22 alkyl group, Ri is selected from H, Cl a alkyl
    C4, R 2 is selected from all the α carbon groups of natural amino acids, R 3 is
    6/28 selected from COOX, CH2-SO3X, X is selected from Li + , Na + or K + ;
    said process comprising the steps of:
    a) the preparation of fatty acid chlorides by means of halogenation of fatty acids, either with phosgene or with thionyl chloride, in the presence of a catalytic amount of the same or another N-acyl amino acid surfactant of Formula I, or anhydrides of surfactant itself, Formula II,
    Ολ / A
    Laugh
    Formula II where, R = C6 to C22 alkyl group, Ri = H, Cl to C4 alkyl, R 2 = all α carbon groups of natural amino acids, n = 0 to 4, X = C, SO and
    b) the reaction of the fatty acid chloride of step (a) with an amino acid in the presence of a base, under typical aqueous conditions of Schotten Baumann, such that the said process does not employ a purification step.
    Detailed description of the invention [0018] The present invention relates to a low cost process for the production of amino acid-based surfactants, using the same surfactants as catalysts for the synthesis of the high quality intermediate and with a quantitative yield .
    [0019] The method of the present invention describes the manufacture of N-acyl amino acid surfactants, of Formula I,
    R1
    Formula I where, R represents the alkyl chain with carbon atoms ranging from 6 to 22, Ri
    7/28 represents H, or small alkyl chains ranging from C1 to C4, R 2 represents all α carbon groups of natural amino acids, R 3 represents an acidic group, such as carboxy or sulfonyl with an alkali metal counter-cation, as in COOX, CH 2 SO3X, where X = Li + , Na + or K + .
    [0020] The process of the present patent application involves two steps. The first stage is the production of fatty acid chloride and, in the second stage, the fatty acid chloride manufactured in the first stage is placed to react with an amino acid in an aqueous solvent medium or in an aqueous mixture, in the presence of base, to obtain the N-acyl amino acid surfactants.
    [0021] The alkyl chain, represented by R, can be either numbered or odd, linear or branched. It can be a single chain or a mixture of several alkyl chains, ranging from C6 to C22. The alkyl chain can be completely saturated or it can be unsaturated, with one or more double bonds. These alkyl chains are derived from fresh fatty acids, mostly in the form of animal fats or vegetable oils. The unsaturated alkyl chains can be derived from oleic acid, recolinoleic acid, linoleic acid, linolenic acid, elaeosteric acid, eicosanoic acid, erucic acid, docosodienoic acid and undecylenic acid. Saturated fatty acids are generally derived from palm oil / palm almond or coconut oil and are all numbered, ranging from octanoic acid (C8) to stearic acid (C18). Fatty acids with the highest number of carbons (C18 to C22) are derived from mustard oil, tung oil and rapeseed oil.
    [0022] Saturated / unsaturated fatty acids are converted into the corresponding acid chlorides, treating them with either thionyl chloride or phosgene. Both reagents react with each other in an equivalent stoichiometric amount or up to 3% excess of the chlorinating agent (mole ratio, fatty acids: chlorinating agent :: 1: 1.03). The halogenations of fatty acids with both phosgene and thionyl chloride are carried out at a temperature between 20 and 45 ° C, under a nitrogen layer, with a washing system for the absorption of HCl and SO2 by-products. At the plant scale, the well-established closed-loop technique can be followed, where SO 2 and HCl are separated and are conveniently used when SO 2 is converted
    8/28 again in SOCl 2 .
    [0023] According to the present invention, the types of amino acids that are used in the synthesis of Formula I compounds are naturally occurring α-amino acids (glycine, alanine, valine, leucine, isoleucine, methionine, proline, cysteine, phenyl alanine, tyrosine, tryptophan, arginine, lysine, histidine, aspartic acid, glutamic acid, serine, threonine, asparagine, glutamine), unnatural amino acids (opposite D stereochemistry), mixtures of stereoisomers, unnatural amino acids (propionic amino acid, N-methyl taurine, sarcosine). In summary, the amino acids required for the synthesis of the compounds of Formula I must have a primary or secondary amino group at one end and an acid group, both carboxylic and sulfonic at the other end.
    [0024] During the synthesis of N-acyl amino acid surfactants, fatty acid chloride is added to a stirred and cooled (10 to 15 ° C) aqueous solution of amino acid, in its salt form, with alkali metals. The cations of the salt form of the amino acids are alkali metal ions, such as potassium, sodium or lithium. For this condensation (Schotten Baumann reaction), the ratio of fatty acid chloride to the amino acid varies from 1: 1 to 1: 1.03. To a stirred and cooled amino acid solution, a base equivalence (in the form of a solution) and a fatty acid chloride equivalence are added simultaneously, maintaining the stoichiometric ratio and the pH of the reaction mass between 10 to 11, preferably between 10.3 to 10.6. The Schotten Baumann reaction is a quick reaction and results in a very clean product, with the generation of stoichiometric by-product, salt, alkali metal chloride, depending on the base used. The small extent of hydrolysis of the fatty acid chloride results in the generation of the corresponding alkali metal salts of fatty acids. The N-acyl products that are obtained are practically colorless and odorless. The products obtained are free of any contamination, due to residual catalysis, since the catalyst used is the same surfactant that is being produced.
    [0025] The present patent application describes the use of N-acyl amino acid catalysts, for the production of fatty acid chloride that would provide the same surfactant after the second stage of the Schotten Baumann reaction. The stage
    9/28 of fatty acid chloride employs 0.05 to 2% moles of N-acyl surfactants as catalysts. In Example No. 4, of experimental section, the synthesis of sodium cocoyl glycinate is obtained using cocoyl chloride, which was generated by the reaction of coconut fatty acid and thionyl chloride, catalyzed by the sodium cocoyl glycinate itself. Similarly, Example No. 6 describes the synthesis of sodium cocoyl glycinate from lauroyl chloride and glycine, in the presence of a base. For this conversion, lauroyl chloride was synthesized from lauric acid and thionyl chloride, under the catalytic influence of sodium lauroyl glycinate.
    [0026] N-acyl surfactants amino acids actually catalyze the reactions of fatty acid halogenations and generally work very efficiently at a concentration level of 0.02 to 2.00 mole%. It is quite possible that the Nacil surfactant amino acids, in its saline form, for example, sodium lauroyl glycinate, (Formula III, R = C11 and R 2 = H) will react with a halogenating agent, giving the Vilsmeier complex, which catalyzes the formation of fatty acid chloride and, once the fatty acid chloride (lauroyl chloride) is formed, it can then react with the sodium salt of the lauryl glycinate to form the N-lauroyl anhydride anhydride glycolic lauric (Formula IV, R = C11, R 2 = H, as shown in scheme 4. Thus Catalyst I, (Formula IV, R = C11, R 2 = H) is produced in situ which can complex with the agent halogenation and form the reactive active catalytic species of the Vilsmeier type, which has phenomenal solubility in fatty reagents, due to the presence of two long alkyl chains on both sides of the anhydride part. perfect for hom catalysis This hypothesis was quickly tested by synthesizing the anhydride, catalyst I (Formula IV, R = C11, R 2 = H) and using it as a catalyst in lauric acid halogenation.
    [0027] The stoichiometric amounts of sodium lauroyl glycinate (Formula III, R = C11, R 2 = H) and lauroyl chloride were stirred in dichloromethane at room temperature for 12 hours. Filtration of the salt yielded the desired N-lauroyl lauric glycolic anhydride as a waxy solid (scheme 4, Formula IV, R = C11, R 2 = H). The infrared spectrum N-lauroyl lauric glycolic anhydride showed the characteristic stretching frequency for the anhydride bond at 1750 and 1817 cm -1 . The NH stretch and the
    10/28 carbonyl stretch appeared at 3294 cm ' 1 and 1643 cm' 1 , respectively.
    [0028] The proton magnetic resonance spectrum, of the same molecule in deuterated chloroform, showed the signal for methylene protons of δ 2.46 glycine fraction.
    [0029] This anhydride, catalyst I (Formula IV, R = Cll, R 2 = H) thus obtained, was then used as a catalyst for the synthesis of lauroyl chloride at the level of 0.13% by moles (scheme No. 5 , Example 1). The lauroyl chloride obtained was practically colorless with very good conversion (Table 1, in Experiment 1). This lauroyl chloride was then used without any purification and was reacted with the stoichiometric amount of glycine in water, at a temperature between 10 to 15 ° C, in the presence of an equivalent amount of base (Experiment 1). The residual catalyst I (Formula IV, R = Cll, R 2 = H) present in the lauroyl chloride can be subjected to nucleophilic attack by glycine, in the next step of the Schotten Baumann reaction, to provide two molecules of sodium lauroyl glycinates. Concurrent nucleophilic water (alkaline pH) can hydrolyze the anhydride to produce sodium lauroyl glycinate and sodium laurate. The final product, which is an aqueous solution of sodium lauroyl glycinate with a content of 30% solids, will have 0.0002 mol% of sodium laurate, generated by hydrolysis of the anhydride catalyst. In the presence of a better nucleophile, in the form of glycine, it seems very unlikely that the residual catalyst (Formula IV, R = Cll, R 2 = H) in lauroyl chloride will undergo exclusively alkaline hydrolysis.
    R
    COONa
    R
    R = Ci to C22
    R2 = H, Ci to C4
    Layout 4
    Formula III
    Formula IV, Catalyst I
    SOCb
    + Catalyst I
    COOH + Catalyst I
    NaOH / water
    Schotten Baumann
    Layout 5
    11/28 [0030] The rate of catalysis of lauroyl chloride formation, from lauric acid and thionyl chloride, as well as sodium lauroyl glycinate (Formula III, R = Cll, R 2 = H) or N- lauroyl glycolic lauric anhydride (Formula IV, R = Cll, R 2 = H) showed to be qualitatively the same at the same percentage in moles.
    [0031] In addition, sodium lauroyl glycinate, the surfactant of N-acyl amino acids, prepared from the lauroyl chloride obtained as above, using either sodium lauroyl glycinate (Formula III, R = Cll, R 2 = H) , as a catalyst, either N-lauroyl lauric glycolic anhydride (formula III, R = C12, R 2 = H), as a catalyst, provide the surfactant with the same quality.
    R = Ci to C22
    Rz = H, Ci to C-i
    Formula V
    Form u Catalyst II
    Catalyst II _ ç | _ | 3
    Layout 6
    R
    Catalyst II
    NaOH Water
    SOaNa
    Catalyst II
    Scholten Baumann
    Scheme 7 + NaCI
    The fatty acid chlorination catalysis was confirmed with other N-acyl surfactants, such as sodium lauroyl, N-methyl taurate (Experiment No. 7) (Formula IV, R = C12, R 2 = CH3 scheme 6) and using The tauronic lauric anhydride (Experiment No. 2, Formula VI, R = Cll, R 2 = CH 3 scheme 7). The lauroyl chloride with residual catalyst (mixed anhydride of Formula V), thus obtained, was converted into lauroyl, N-methyl taurate of
    12/28 sodium, through its reaction with sodium N-methyl taurate, under aqueous conditions of Schotten Baumann.
    [0032] According to the present invention any N-acyl amino acid surfactant can essentially catalyze the chlorination of any fatty acid or fatty acid mixture, to obtain the corresponding fatty acid chlorides, at a concentration level of 0 , 02 to 2.0 mole%. Example 8 shows an easy synthesis of sodium cocoyl glycinate, where the synthesis of cocoyl chloride is obtained by catalyzing the reaction between coconut fatty acid and thionyl chloride by N-lauroyl, N-methyl taurate.
    [0033] It is evident, for those with knowledge of the prior art, that the fatty acid chlorides thus produced are not only suitable for a discontinuous process of Schotten Baumann reaction, but also for a continuous process of production of N- acyl amino acids, by the reaction of fatty acid chlorides, amino acid salts and the bases.
    [0034] According to the invention, the described process is very cost-effective, since it avoids the purification steps, which results in a significant reduction in energy consumption. The process of the present invention also avoids laborious purification steps and product loss caused by the purification steps.
    [0035] According to another embodiment of the invention, the process avoids all toxic catalysts used in the state of the art. The two-stage process does not affect the environment at all, since it does not generate effluents (waste is not eliminated), consumes less energy, covers fewer operations, provides quantitative yields and, above all, uses a catalyst biodegradable compatible eco. In summary, the present patent application describes a synthesis of self-catalyzing N-acyl amino acid surfactant.
    [0036] The above-described features, benefits and advantages of the present invention will be appreciated and understood by those skilled in the art by the following detailed description and claims.
    [0037] Advantages of the invention:
    1) the use of the same N-acyl surfactants amino acids to catalyze the
    13/28 main stage (the precursor), in the production of N-acyl surfactants amino acids;
    2) the catalyst for the acid chloride intermediate is the surfactant itself being produced and, therefore, the fatty acid chloride intermediate does not have to be purified through additional steps (distillation / crystallization), which often lead to loss substantial yield and increased production cycle time, as well as increased energy consumption;
    3) unlike the prior art processes, the process of the present invention uses a completely degradable catalyst for the production of intermediate acid chlorides;
    4) N-acyl amino acid surfactant catalysts work equally well with both industrial halogenating agents. These catalysts work very well with phosgene and thionyl chloride during the production of fatty acid chloride. The phosgenation by-product is CO 2 whereas, with thionyl chloride, the by-product is SO 2 , which can be converted into surfuryl chloride and subsequently thionyl chloride through a well-established closed-loop chemistry ' (United States patent 5,489,400);
    5) once the distillation / crystallization phase separation steps are carried out, during the production of fatty acid chloride, there is no generation of effluents and, consequently, in addition to the advantage of lower energy consumption, there is a significant savings in waste disposal. Thus, the N-acyl amino acid surfactant production process of the present patent application is completely eco-sustainable and nothing is thrown into the environment;
    6) unlike state of the art processes, the process of the present patent application does not use any toxic catalysts and, therefore, the problem of isolating the toxic catalyst product does not exist;
    7) the process of the present patent application uses non-toxic and biodegradable catalysts. The process involves less chemical engineering and offers high throughput with quantitative conversions and throughput. This provides a cost-effective, eco-friendly and sustainable process.
    EXAMPLES
    14/28 [0038] The present invention will now be described by means of illustrative examples. The following examples are presented illustratively in greater detail, however the invention is not limited to the examples.
    [0039] Fatty acids were purchased from Natural Oleo-Chemicals, Malaysia, while thionyl chloride was purchased from Transpek Industries, Vadodara, India. The phosgene trimer, glycine and sodium N-methyl taurate were purchased from Aldrich.
    [0040] The color value is used as an indication of the degree of purity of the acid chloride product. The color value of N-acyl amino acid intermediates and surfactants was determined on an APHA scale by Lovibond PFX995 / 950. The chlorides of fatty acids were analyzed according to the analytical method described in Quantitative Organic Analysis Via Functional Groups, Ed Sidney Siggia and Hanna J. Graxon, 4th Edition (Pag. 223-230), John Wiley & Sons (1979) .
    Example 1
    Preparation of sodium lauroyl glycinate [0041] It consists of three stages: a) preparation of Catalyst I: N-lauroyl lauryl glycolic anhydride (Formula IV, RCO = lauroyl, R = C11), b) preparation of lauroyl chloride, using o Catalyst I and c) preparation of sodium lauroyl glycinate: Schotten Baumann reaction of lauroyl chloride with glycine, in the presence of a base.
    Preparation of Catalyst I: N-lauroyl glycolic lauric anhydride (Formula IV, RCO = lauroyl, R = C11).
    [0042] To a stirred mass of lauroyl chloride (6.0 g, 0.027 gmol), in dichloromethane (25 ml), under a nitrogen layer, at 25 ° C, sodium lauroyl glycinate was slowly added in a cool oven (7.50 g, 0.027 gmol) and the reaction mass was stirred for 12 hours. The reaction mass was filtered and the solvent was removed, in vacuo, using a rotary evaporator, to produce a white solid residue (9.4 g). The white residue has a melting range of 125 to 130 o C.
    IR: 1643 cm -1 of amide CO, 3294 cm -1 NH of amide, 1750 and 1817 cm -1 CO of anhydride, 2849, 2917, 2954 cm -1 CH of stretching of the alkyl chain;
    NMR: (CDCh): δ 0.86 to 0.89 (6H of two methyl groups of the lauryl chains), 1.25 to 1.29 (34 H, methylenes of alkyl chains), 1.63 to 1.67 ( 4 H), 2.46 (2H). The melting range is
    15/28 to 78 o C.
    Preparation of lauroyl chloride using Catalyst I, N-lauroyl glycolic lauryl anhydride (Formula IV, RCO = lauroyl, R = C11).
    [0043] To a stirred mass of lauric acid (200 g, 0.999 gmol) and N-lauroyl glycolic lauric anhydride (Formula IV, RCO = lauroyl, R = C11) from step I (0.6 g, 0.0013 gmol) , at 25 ° C, under a nitrogen layer, thionyl chloride (123 g, 1.03 gmol) was added slowly, at 25 ° C and at atmospheric pressure, over a period of 2 hours, keeping the temperature below 25 ° C. Hydrochloric acid and sulfur dioxide, generated during the process, were intermittently purified in a gas purifier containing caustic liquor. The reaction mixture was stirred for an additional 4 hours at the reaction temperature. The progress of the reaction was monitored, measuring the formation of alkanoyl chloride and residue-free fatty acid (Sidney Siggia and Hanna J. Graxon, Quantitative Organic Analysis Via Functional Groups, 4th Edition (Pag. 223 - 230), John Wiley & Sons (1979)). The nitrogen gas was purged through the reaction mass for 3 hours, in order to remove residual traces of sulfur dioxide, hydrogen chloride gas and unreacted thionyl chloride. At the end of this procedure, lauroyl chloride (214 g, 98.0%) was obtained as an almost colorless product. The detailed analysis is given in table 1.
    Table 1
    Parameters Analyze Appearance Clear liquid Color (APHA scale) 105 % Purity 9.40 % Free fatty acid 2.27
    Preparation of sodium lauroyl glycinate:
    [0044] To a stirred solution of glycine (35 g, 0.47 gmol) in water (300 ml), at a temperature between 10 to 15 ° C, under a hydrogen layer, lauroyl chloride (100 g, 0 , 45 gmol) and sodium hydroxide (36.5 g in 60 ml of water ~ 40% solution, 0.91 gmol), as the pH was maintained from 10.3 to 10.6 for 2 hours. The reaction was continued for an additional 3 hours at
    16/28 between 25 to 30 ° C and maintaining the same pH range and, finally, the total weight was adjusted to 510 g by adding water in order to obtain the aqueous solution of sodium lauroyl glycinate, with the result at below, as shown in table 2.
    Table 2
    Parameters Analyze Appearance Clear liquid Color (APHA scale) 75 % solids 30.1 % sodium laurate 1.5 Viscosity 1650 Cps % Sodium chloride 5.03
    Example 2
    Preparation of N-lauroyl, sodium N-methyl taurate:
    [0045] It consists of three steps: a) preparation of catalyst II: mixture of N-lauroyl, N-methyl lauric anhydride, taurine (Formula VI, RCO = lauroyl, R = C12), b) preparation of lauryl chloride using catalyst II and c) preparation of N-lauroyl, sodium N-methyl taurate: Schotten Baumann reaction of lauroyl chloride with sodium N-methyl taurate, in the presence of a base.
    Preparation of catalyst II: mixture of N-lauroyl, N-methyl lauric lauric anhydride (Formula VI, RCO = lauroyl, R = C11).
    [0046] To a stirred mass of lauroyl chloride (6.0 g, 0.027 gmol), in dichloromethane (25 ml), under nitrogen layer, at 25 ° C, N-lauroyl, Nmethyl sodium taurate ( 9.28 g, 0.027 gmol) dried in a cool oven and the reaction mass was stirred for 12 hours. The reaction mass was filtered and the solvent was removed in vacuo, using a rotary evaporator to produce a white solid residue (14 g).
    IR: 1636 cm -1 of CO amide, 1723 and 1801 cm -1 CO of anhydride, 2850, 2920, 2956 cm -1 CH of stretching of the alkyl chain, 1173 and 1207 cm -1 SO 2 - Preparation of lauryl chloride using catalyst II: mixture of N-lauroyl, N-methyl lauric lauric anhydride (Formula VI, RCO = lauroyl, R = C12).
    [0047] To a stirred mass of lauric acid (200 g, 0.999 gmol) and N-lauroyl mixture,
    17/28
    N-methyl lauric lauric anhydride (Formula V, RCO = lauroyl, C12) from step I (0.6 g, 0.0012 gmol), at 25 ° C, under a nitrogen layer, thionyl chloride (123 g , 1.03 gmol), at 25 ° C and atmospheric pressure, for a period of 2 hours, keeping the temperature below 25 ° C. The hydrochloric acid and sulfur dioxide generated during the process were continuously purified in a purifier. of gases containing caustic bleach. The reaction mixture was stirred for an additional 4 hours at the reaction temperature. The progress of the reaction, in the last phase, was monitored by measuring the formation of alkanoyl chloride. The nitrogen gas was purged through the reaction mass for 3 hours in order to remove residual traces of sulfur dioxide, hydrogen chloride gas and unreacted thionyl chloride. At the end of this procedure, lauroyl chloride (212 g, 97%) was obtained as an almost colorless product. The detailed analysis is given in the table
    3.
    Table 3
    Parameters Analyze Appearance Clear liquid Color (APHA scale) 85 % Purity 98.00 % Free fatty acid 1.57
    Preparation of N-lauroyl, sodium N-methyl taurate.
    [0048] To a stirred solution of sodium N-methyl taurate (74 g, 0.46 gmol) in water (450 ml) at a temperature between 10 and 15 ° C, under a nitrogen layer, lauroyl chloride ( 100 g, 0.45 gmol) and sodium hydroxide (18 g in 30 ml of water ~ 40% solution, 0.45 gmol), as the pH was maintained between 10.3 to
    10.6 for 4 hours. The reaction was continued for an additional 3 hours at a temperature between 25 to 30 o C and maintaining the same pH. Finally, the total weight was adjusted to 640 g in order to obtain an aqueous solution of N-lauroyl, sodium N-methyl taurate with the analysis shown in table 4.
    Table 4
    18/28
    Parameters Analyze Appearance Clear liquid Color (APHA scale) 125 % Solid 30.11 % Sodium Cocoate 1.5 Viscosity 150 Cps % Sodium chloride 4.1
    Example 3
    Preparation of sodium cocoyl glycinate.
    [0049] It consists of three stages: a) preparation of Catalyst I: N-cocoyl glycolic cocoic anhydride (Formula IV, RCO = cocoyl, R = C6 to C18) b) preparation of cocoyl chloride using Catalyst I and c) preparation of sodium cocoyl glycinate: Schotten Baumann reaction of cocoyl chloride with glycine, in the presence of a base.
    [0050] Coconut fatty acid, which was used to make catalyst I (N-cocoyl glycolic glycolic anhydride (Formula IV, RCO = cocoyl, R = C6 to C18), as well as to make cocoyl chloride had the following composition :
    C 8 (caprylic acid) - 5.38%
    C 10 (capric acid) - 5.78%
    C 12 (lauric acid) - 61.37%
    C 14 (myristic acid) - 20.77%
    C 16 (palmitic acid) -4.7% and
    C 18 (stearic acid) -2.0%
    Preparation of Catalyst I: N-cocoyl glycolic glycolic anhydride (Formula IV, RCO = cocoyl, C8 to C18).
    [0051] To a stirred mass of cocoyl chloride (10 g, 0.045 gmol), in dichloromethane (50 ml), under a nitrogen layer, at 25 ° C, sodium cocoyl glycinate (12.5 g, 0.045) was slowly added gmol) dried in a cool oven and the reaction mass was stirred for 12 hours. The reaction mass was filtered and the solvent was removed in vacuo, using a rotary evaporator to obtain the anhydride as a white solid residue (20 g).
    IR: 1,645 cm -1 of amide CO, 3206 cm -1 NH of amide, 1750 and 1816 cm -1 CO of
    19/28 anhydride, 2849, 2917.2954 cm -1 CH of alkyl chain stretch
    Preparation of cocoyl chloride using Catalyst I, N-cocoyl glycolic glycolic anhydride (Formula IV, RCO = cocoyl, R = C6 to C18).
    [0052] To a stirred mass of coconut fatty acid (200 g, 0.99 gmol) and N-cocoyl glycolic glycolic anhydride (Formula IV, RCO = cocoyl, R = C6 to C18) from step I, (0.6 g, 0.0013 gmol), at 25 ° C, under a nitrogen layer, thionyl chloride (123 g, 1.03 gmol) was added slowly. at 25 ° C and atmospheric pressure. over a period of 2 hours, keeping the temperature below 25 ° C. The hydrochloric acid and sulfur dioxide generated during the process were continuously purified in a gas purifier containing caustic liquor. The reaction mixture was stirred for an additional 4 hours at the reaction temperature. The progress of the reaction was monitored, measuring the formation of alkanoyl chloride. The nitrogen gas was purged through the reaction mass for 3 hours to remove residual traces of sulfur dioxide, hydrogen chloride gas and unreacted thionyl chloride. At the end of this procedure, cocoyl chloride (212 g, 97%) was obtained as an almost colorless product. The detailed analysis is given in table 5.
    Table 5
    Parameters Analyze Appearance Clear liquid Color (APHA scale) 85 % Purity 98.6 % Free fatty acid 1.35
    Preparation of sodium cocoyl glycinate.
    [0053] To a stirred solution of glycine (35.0 g, 0.47 gmol) in water (300 ml) at a temperature between 10 and 15 O C, under a nitrogen layer, were added simultaneously cocoyl chloride (100 g, 0.45 gmol) and sodium hydroxide (36.5 g in 60 ml, ~ 40% solution, 0.91 gmol), as the pH was maintained between 10.3 to 10.6 for 4 hours. The reaction was continued for an additional 3 hours, maintaining the same pH variation, and the final weight was adjusted to 510 g in order to obtain an aqueous solution of sodium cocoyl glycinate, with the following analysis, as shown in the table 6.
    20/28
    Table 6
    Parameters Analyze Appearance Clear liquid Color (APHA scale) 125 % Solid 29.98 % Sodium Cocoate 1.67 Viscosity 1200 Cps % Sodium chloride 4.93
    Example 4
    Preparation of sodium cocoyl glycinate: two-step procedures: generation of catalyst in situ:
    [0054] Preparation of sodium cocoyl glycinate by a two-step process comprising: a) preparation of cocoyl chloride, coconut fatty acid and thionyl chloride, in the presence of a catalytic amount of sodium cocoyl glycinate and b) preparation of sodium cocoyl glycinate from the cocoyl chloride of step (a) and glycine, in aqueous medium.
    Preparation of cocoyl chloride from coconut fatty acid and thionyl chloride, in the presence of a catalytic amount of sodium cocoyl glycinate.
    [0055] Coconut fatty acid, which was used to make catalyst I (N-cocoyl glycolic glycolic anhydride (Formula IV, RCO = cocoyl, C6 to C18), as well as to make cocoyl chloride, had the following composition:
    C 8 (caprylic acid) - 5.38%
    C 10 (capric acid) - 5.78%
    C 12 (lauric acid) -61.37%
    C14 (myristic acid) - 20.77%
    C 16 (palmitic acid) - 4.7% and
    C 18 (stearic acid) -2.0%
    Preparation of cocoyl chloride by insitu generation of Catalyst I, N-cocoyl glycolic cocoic anhydride (Formula IV, RCO = cocoyl, R = C6 to C18) [0056] To a stirred mass of coconut fatty acid (200 g, 0, 99 gmol) and glycinate of
    21/28 sodium cocoyl (0.6 g, 0.002 gmol), at 25 ° C, under nitrogen layer, thionyl chloride (123 g, 1.03 gmol) was added slowly at 25 ° C and at atmospheric pressure , for a period of 2 hours, keeping the temperature below 25 ° C. The hydrochloric acid and sulfur dioxide generated during the process were continuously purified in a gas purifier containing caustic liquor. The reaction mixture was stirred for an additional 4 hours at the reaction temperature. The progress of the reaction was monitored by measuring the formation of alkanoyl chloride. The nitrogen gas was purged through the reaction mass for 3 hours to remove residual traces of sulfur dioxide, hydrogen chloride gas and unreacted thionyl chloride. At the end of this procedure, cocoyl chloride (218 g, 98.8%) was obtained as a virtually colorless product. The detailed analysis is given in table 7.
    Table 7
    Parameters Analyze Appearance Clear liquid Color (APHA scale) 92 % Purity 98.45 % Free fatty acid 1.2
    Preparation of sodium cocoyl glycinate from the cocoyl chloride of step (a) and glycine, in aqueous medium
    Preparation of sodium cocoyl glycinate [0057] To a stirred solution of glycine (35 g, 0.47 gmol) in water (300 ml), at a temperature between 10 and 15 ° C, under a nitrogen layer, simultaneously added chloride cocoyl (100 g, 0.45 gmol) and sodium hydroxide (36.5 g in 60 ml of water, ~ 40% solution, 0.91 gmol), as the pH was maintained between 10.3 to
    10.6 for 4 hours. The reaction was continued for an additional 3 hours, maintaining the same pH variation. Finally, the weight was adjusted to obtain 510 g of aqueous sodium cocoyl glycinate solution, according to the following analysis, as given in table 8.
    Table 8
    22/28
    Parameters Analyze Appearance Clear liquid Color (APHA scale) 112 % Solid 30 % Sodium Cocoate 1.78 Viscosity 1250 Cps % Sodium chloride 5.2
    Example 5
    Preparation of sodium lauroyl sarcosinate [0058] It consists of two steps: a) preparation of lauroyl chloride using sodium lauroyl sarcosinate and b) preparation of sodium lauroyl sarcosinate: Schotten Baumann reaction of lauroyl chloride with sodium sarcosinate, na presence of a base.
    Preparation of lauroyl chloride using sodium lauroyl sarcosinate as a catalyst.
    [0059] To a stirred mass of lauric acid (200 g, 1.0 gmol) and sodium N-lauroyl sarcosinate (0.6 g, 0. 002 gmol), at 25 ° C, under a nitrogen layer, was added slowly thionyl chloride (123 g, 1.03 gmol), at 25 ° C and atmospheric pressure, over a period of 2 hours, keeping the temperature below 25 ° C. The hydrochloric acid and sulfur dioxide generated during the process were purged in a gas purifier containing caustic bleach. The reaction mixture was stirred for an additional 4 hours at the reaction temperature. The progress of the reaction was monitored by measuring the formation of alkanoyl chloride after completion of the addition.
    [0060] The nitrogen gas was purged through the reaction mass for 3 hours to remove residual traces of sulfur dioxide, hydrogen chloride gas and unreacted thionyl chloride. At the end of this procedure, lauroyl chloride (213 g, 97.5%) was obtained as an almost colorless product. The detailed analysis is given in table 9.
    23/28
    Table 9
    Parameters Analyze Appearance Clear liquid Color (APHA scale) 150 % Purity 97.40 % Free fatty acid 2.27
    Preparation of sodium lauroyl sarcosinate:
    [0061] To a stirred solution of sodium sarcosinate (52 g, 0.47 mmol) in water (330 ml), at a temperature between 10 to 15 ° C, under a nitrogen layer, lauroyl chloride (100 g) was added simultaneously , 0.45 mmol) and sodium hydroxide (18.0 g in 60 ml of water, ~ 40% solution, 0.455 mmol), as the pH was maintained between 10.3 to 10.6 for 2 hours . The reaction was continued for an additional 3 hours at a temperature between 25 to 30 °, maintaining the same pH variation and the final weight was adjusted to obtain 540 g of aqueous sodium lauroyl sarcosinate solution, with the following analysis, as given in table 10.
    Table 10
    Parameters Analyze Appearance Clear liquid Color (APHA scale) 125 % Solid 30.3 % Sodium laurate 1.76 Viscosity 700 Cps % Sodium Chloride 4.72
    Example 6
    Preparation of sodium lauroyl glycinate: two-step procedure: catalyst generation in situ:
    [0062] Preparation of sodium lauroyl glycinate by a two-step procedure, comprising a) preparation of lauroyl chloride from lauric acid and thionyl chloride, in the presence of a catalytic amount of sodium lauryl glycinate and b)
    24/28 preparation of sodium lauroyl glycinate from lauroyl chloride from step (a) and glycine, in aqueous medium.
    Preparation of lauroyl chloride by in-situ generation of Catalyst I, N-lauroyl glycolic lauric anhydride (Formula IV, RCO = lauroyl, R = C 11).
    [0063] To a stirred mass of lauric acid (200 g, 1.0 gmol) and sodium lauroyl glycinate (0.6 g, 0.002 gmol), at 25 ° C, under a nitrogen layer, thionyl chloride was slowly added (123 g, 1.03 gmol), at 25 ° C and atmospheric pressure, for a period of 2 hours, keeping the temperature below 25 ° C. The hydrochloric acid and sulfur dioxide generated during the process were continuously purged in a gas purifier containing caustic bleach. The reaction mixture was stirred for an additional 4 hours at the reaction temperature. The progress of the reaction was monitored by measuring the formation of alcohol chloride. The hydrogen gas was purged through the reaction mass for 3 hours to remove residual traces of sulfur dioxide, hydrogen chloride gas and unreacted thionyl chloride. At the end of this procedure, lauroyl chloride (218 g, 99.8%) was obtained as an almost colorless product. The detailed analysis is given in table 11.
    Table 11
    Parameters Analyze Appearance Clear liquid Color (APHA scale) 85 % Purity 98.5 % Free fatty acid 1.56
    Preparation of sodium lauroyl glycinate from the lauroyl chloride from step (a) and glycine, in aqueous medium.
    Preparation of sodium lauroyl glycinate:
    [0064] To a stirred solution of glycine (35 g, 0.47 gmol) in water (300 ml), at a temperature between 10 to 15 ° C, under a nitrogen layer, lauroyl chloride (100 g, 0.457) were added simultaneously gmol) and sodium hydroxide (36.5 g in 60 ml of water, ~ 40% solution, 0.91gmol), as the pH was maintained between
    25/28
    10.3 to 10.6 for 4 hours. The reaction was allowed to return to room temperature and continued for an additional 3 hours, at a temperature between 25 to 30 o C, maintaining the same pH range and, finally, the weight was adjusted to obtain 520 g of solution aqueous sodium lauroyl glycinate, with the following analysis, as given in table 12.
    Table 12
    Parameters Analyze Appearance Clear liquid Color (APHA scale) 125 % Solid 30 % Sodium laurate 1.5 Viscosity 1600 Cps % Sodium chloride 4.9
    Example 7
    Preparation of N-lauroyl, sodium N-methyl taurate: two-step procedure: generation of the catalyst in situ.
    [0065] Preparation of sodium N-lauroyl, N-methyl taurate by a two-step procedure comprising a) preparation of lauroyl chloride from lauric acid and thionyl chloride in the presence of N-lauroyl, N-methyl sodium taurate and b) Schotten Baumann reaction of lauroyl chloride from step (a) with sodium N-methyl taurate, in the presence of a base.
    Preparation of lauroyl chloride by in-situ generation of Catalyst II, N-lauroyl, N-methyl lauric anhydride mixture (Formula VI, RCO = lauroyl, R = C11).
    [0066] To a stirred mass of lauric acid (200 g, 0.999 gmol) and N-lauroyl, N-methyl taurate sodium (0.6 g, 0.0017gmol), at 25 ° C, under a nitrogen layer, was added slowly thionyl chloride (123 g, 1.03 gmol), at 25 ° C and atmospheric pressure, over a period of 2 hours, keeping the temperature below 25 ° C. The hydrochloric acid and sulfur dioxide generated during the process were continuously purified in a gas purifier containing caustic bleach. The reaction mixture was stirred for 4
    Additional 26/28 hours at the reaction temperature. The progress of the reaction in the last phase was monitored, measuring the formation of alkanoyl chloride. The nitrogen gas was purged through the reaction mass for 3 hours to remove residual traces of sulfur dioxide, hydrogen chloride gas and unreacted thionyl chloride. At the end of this procedure, lauroyl chloride (212 g, 97%) was obtained as an almost colorless product. The detailed analysis is given in table 13.
    Table 13
    Parameters Analyze Appearance Clear liquid Color (APHA scale) 85 % Purity 98.00 % Free fatty acid 1.57
    Preparation of N-lauroyl, sodium N-methyl taurate.
    [0067] To a stirred solution of sodium N-methyl taurate (74 g, 0.46 gmol) in water (400 ml), at a temperature between 10 to 15 ° C, under a nitrogen layer, lauroyl chloride was added simultaneously (100 g, 0.45 gmol) and sodium hydroxide (18 g in 30 ml of water, ~ 40% solution, 0.45 gmol), as the pH was maintained between 10.3 to
    10.6 for 4 hours. The reaction was allowed to return to room temperature and continued for an additional 3 hours at a temperature between 25 to 30 ° C, maintaining the pH, and finally the weight was adjusted to obtain 602 g of aqueous N solution -lauroyl, Nmethyl sodium taurate, with the following analysis, as shown in table 14.
    Table 14
    Parameters Analyze Appearance Clear liquid Color (APHA scale) 125 % Solid 30 % Sodium laurate 1.5 Viscosity 100 Cps % Sodium chloride 4.2
    27/28
    Example 8
    Preparation of sodium cocoyl glycinate: two-step procedure: generation of the catalyst in situ:
    [0068] Preparation of sodium cocoyl glycinate by a two-step process comprising a) preparation of cocoyl chloride from coconut fatty acid and thionyl chloride, in the presence of a catalytic amount of N-cocoyl, N- sodium methyl taurate and b) preparation of sodium cocoyl glycinate from the cocoyl chloride of step (a) and glycine, in aqueous medium.
    Preparation of cocoyl chloride from coconut fatty acid and thionyl chloride in the presence of a catalytic amount of N-cocoyl, sodium N-methyl taurate.
    [0069] Coconut fatty acid, which was used to produce cocoyl chloride, had the following composition:
    C 8 (caprylic acid) - 5.38%
    C10 (capric acid) - 5.78% C12 (lauric acid) -61.37% C14 (myristic acid) - 20.77% C 16 (palmitic acid) -4.7% and C18 (stearic acid) -2, 0%
    Preparation of cocoyl chloride by unsubstantiated generation of Catalyst II, N-cocoyl taurinic cocoic anhydride (Formula VI, RCO = cocoyl, R = C6 to C18, R2 = methyl) [0070] To a stirred mass of coconut fatty acid (200 g, 1.0 gmol) and N-cocoyl, N-methyl taurate sodium (0.6 g, 0.0017 gmol), at 25 ° C, under a nitrogen layer, thionyl chloride (123 g , 1.029 gmol), at 25 ° C and atmospheric pressure, for a period of 2 hours, keeping the temperature below 25 ° C. The hydrochloric acid and sulfur dioxide generated during the process were continuously purged in a gas purifier containing caustic bleach. The reaction mixture was stirred for an additional 4 hours at the reaction temperature. The progress of the reaction was monitored, measuring the formation of alkanoyl chloride. The nitrogen gas was purged through the reaction mass for 3 hours to remove residual traces of sulfur dioxide, hydrogen chloride gas and non-thionyl chloride.
    Reacted. At the end of this procedure, cocoyl chloride (218 g, 100%) was obtained as an almost colorless product. The detailed analysis is given in table 15.
    Table 15
    Parameters Analyze Appearance Clear liquid Color (APHA scale) 78 % Purity 98.56 % Free fatty acid 1.00
    Preparation of sodium cocoyl glycinate from the cocoyl chloride of step (a) and glycine, in aqueous medium
    Preparation of sodium cocoyl glycinate.
    [0071] To a stirred solution of glycine (35 g, 0.47 gmol) in water (300 ml), at a temperature between 10 to 15 ° C, under a nitrogen layer, cocoyl chloride (100 g, 0 , 45 gmol) and sodium hydroxide (36.5 g in 60 ml of water, ~ 40% solution, 0.91 gmol), as the pH was maintained between 10.3 to
    10.6 for 4 hours. The reaction was continued for another 3 hours, maintaining the same pH variation. Finally, the weight was adjusted to obtain 520 g of aqueous sodium cocoyl glycinate solution, with the following analysis, as shown in table 16.
    Table 16
    Parameters Analyze Appearance Clear liquid Color (APHA scale) 112 % Solid 30.1 % Sodium Cocoate 1.58 Viscosity 1330 Cps % Sodium chloride 5.12
    1/2
    权利要求:
    Claims (7)
    [1]
    Claims
    1. Production process of surfactants based on N-acyl amino acids of the Formula

    Laugh
    Formula I characterized by the fact that, R is selected from the C6 to C22 alkyl group, Ri is selected from H, Cl to C4 alkyl, R 2 is selected from all the α carbon groups of natural amino acids, R 3 is selected from COOX , CH 2 -SO 3 X, X is selected from Li + , Na + or K + ;
    the referred process comprising the steps of:
    A) the preparation of fatty acid chlorides by halogenation of fatty acids with thionyl chloride, in the presence of a catalytic amount of the same or another N-acyl amino acid surfactant of Formula I, or anhydrides of the same surfactant, Formula Π,
    D λ

    Laugh
    Formula II where, R = C6 to C22 alkyl group, Ri = H, Cl to C4 alkyl, R 2 = all α carbon groups of natural amino acids, n = 0 to 4, X = C, SO and
    B) the reaction of fatty acid chloride from step (A) with an amino acid, in the presence of a base, under typical aqueous conditions of Schotten Baumann.
    [2]
    2. Process, according to claim 1, characterized by the fact that the catalytic amount of compounds of Formula I and Formula II, is 0.05 to 0.5% by weight based on fatty acid.
    [3]
    3. Process, according to claim 1, characterized by the fact that the
    2/2 amino acids used in the synthesis of Formula I compounds are selected from naturally occurring αamino acids.
    [4]
    4. Process according to claims 1 and 3, characterized by the fact that naturally occurring α-amino acids are selected from glycine, alanine, valine, leucine, isoleucine, methionine, proline, cysteine, phenyl alanine, tyrosine, tryptophan, arginine , lysine, histidine, aspartic acid, glutamic acid, serine, threonine, aspergine and glutamine.
    [5]
    5. Process, according to claim 1, characterized by the fact that the amino acids used in the synthesis of the compounds of Formula I are selected from unnatural amino acids and mixtures of stereoisomers.
    [6]
    6. Process, according to claims 1 and 5, characterized by the fact that unnatural amino acids are selected from propionic amino acid, N-methyl taurine and sarcosine.
    [7]
    7. Process, according to claim 1, characterized by the fact that the halogenations of fatty acids with thionyl chloride are carried out at a temperature between 20 to 45 ° C.
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    同族专利:
    公开号 | 公开日
    ES2597033T3|2017-01-13|
    US9187407B2|2015-11-17|
    ES2597033T5|2020-01-30|
    EP2888226B2|2019-07-03|
    CN104640839A|2015-05-20|
    US20150141682A1|2015-05-21|
    RU2015100215A|2016-08-10|
    BR112015003383A2|2017-07-04|
    CN104640839B|2017-02-15|
    RU2624026C2|2017-06-30|
    EP2888226A1|2015-07-01|
    EP2888226B1|2016-07-20|
    WO2014030038A1|2014-02-27|
    JP6087438B2|2017-03-01|
    JP2015526460A|2015-09-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2790779A|1953-07-27|1957-04-30|Geigy Chem Corp|Rust preventive compositions containing monoamidocarboxylic acids|
    US3318950A|1963-12-10|1967-05-09|Du Pont|Process for preparing carboxylic acid chlorides|
    IT995980B|1973-10-18|1975-11-20|Aquila Spa|USE OF STARCH ACIDS IN THE MAKING OF FLUIDS WATER YES FOR THE PROCESSING OF METALS|
    FR2337121B1|1975-12-31|1978-07-28|Poudres & Explosifs Ste Nale|HOT PHOSGENATION OF ACIDS TO ACID CHLORIDES WITH CARBOXYLIC ACID DIAMIDES AS CATALYSTS|
    EP0340706B1|1988-05-03|1993-10-13|BASF Aktiengesellschaft|Process for the preparation of carboxylic-acid chlorides|
    US5166427A|1988-10-31|1992-11-24|Basf Aktiengesellschaft|Preparation of acyl chlorides|
    US5247105A|1989-12-22|1993-09-21|Unilever Patent Holdings B.V.|Fatty acid halogenide manufacture|
    US5200560A|1990-04-21|1993-04-06|Basf Aktiengesellschaft|Preparation of carboxylic chlorides|
    JPH04149163A|1990-10-09|1992-05-22|Nippon Oil & Fats Co Ltd|Production of n-acylamino acid salt solution|
    US5278328A|1991-03-12|1994-01-11|Nippon Oil & Fats Co., Ltd.|Process for producing carboxylic acid chloride|
    JP2923101B2|1991-10-22|1999-07-26|三井化学株式会社|Method for producing N-long-chain acylamino acid type surfactant|
    US5489400A|1993-04-22|1996-02-06|Industrial Technology Research Institute|Molecular complex of conductive polymer and polyelectrolyte; and a process of producing same|
    DE4324605A1|1993-07-22|1995-01-26|Basf Ag|Process for the production of carboxylic acid chlorides|
    JP3362468B2|1993-08-25|2003-01-07|味の素株式会社|Process for producing N-mixed saturated fatty acyl neutral amino acids|
    JP4392884B2|1998-12-28|2010-01-06|旭化成ケミカルズ株式会社|N-long chain acyl acidic amino acid salt and method for producing the same|
    DE19943844A1|1999-09-13|2001-03-15|Basf Ag|Process for the production of carboxylic acid chlorides|
    DE19943858A1|1999-09-13|2001-03-15|Basf Ag|Process for the purification of carboxylic acid chlorides|
    US6703517B2|2001-11-26|2004-03-09|Ajinomoto Co., Inc.|Method for preparing N-long chain acyl neutral amino acid|
    DE102004048324A1|2003-10-08|2005-05-12|Ajinomoto Kk|Crystals of N-long chain acylglycine salts, processes for their preparation and detergent compositions containing these crystals|
    DE102007055265A1|2007-11-20|2009-05-28|Clariant International Ltd.|Process for the preparation of acylglycinates|
    US8778864B2|2010-11-15|2014-07-15|Johnson & Johnson Consumer Companies, Inc.|Polyglyceryl compounds and compositions|EP2855651B1|2012-05-30|2016-11-02|Clariant International Ltd|N-methyl-n-acylglucamine-containing composition|
    WO2013178671A2|2012-05-30|2013-12-05|Clariant International Ltd.|Use of n-methyl-n-acylglucamines as solubilizers|
    DE102012021647A1|2012-11-03|2014-05-08|Clariant International Ltd.|Aqueous adjuvant compositions|
    CN105263582B|2013-04-20|2018-12-21|克拉里安特国际有限公司|Comprising oil body, fatty acid, amino acid surfactant and N- methyl-N- acyl glucamides composition|
    US9308156B2|2013-05-08|2016-04-12|Galaxy Surfactants Ltd.|Blends of O-acyl-isethionates and N-acyl amino acid surfactants|
    CN103435509B|2013-08-21|2016-03-16|南京华狮化工有限公司|The preparation method of a kind of N-acyl acidic amino acid or its salt and application thereof|
    CN103880646A|2014-03-13|2014-06-25|东力（南通）化工有限公司|Hydrolysis-resistant rectifying process of isovaleryl chloride|
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    法律状态:
    2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-05-28| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2019-12-10| B09A| Decision: intention to grant|
    2020-02-04| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/09/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    IN2453MU2012|2012-08-23|
    PCT/IB2012/055197|WO2014030038A1|2012-08-23|2012-09-28|Method to produce n-acyl amino acid surfactants using n-acyl amino acid surfactants or the corresponding anhydrides as catalysts|
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