CN116635367A - Method for converting disulfide into conversion product and method for producing cysteine - Google Patents
Method for converting disulfide into conversion product and method for producing cysteine Download PDFInfo
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- CN116635367A CN116635367A CN202180083464.1A CN202180083464A CN116635367A CN 116635367 A CN116635367 A CN 116635367A CN 202180083464 A CN202180083464 A CN 202180083464A CN 116635367 A CN116635367 A CN 116635367A
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Abstract
Embodiments of the present disclosure generally relate to methods of converting disulfides to conversion products and methods of producing cysteines. In one embodiment, a method of converting cystine to a conversion product is provided. The method includes introducing an organic peroxide and water into cystine to form a mixture. The method further comprises reacting the mixture under conversion conditions to form a conversion product, wherein the conversion product comprises cysteine, the amount of cysteine in the conversion product is greater than about 90wt% based on the total weight of the conversion product, and the conversion conditions comprise a conversion temperature of about 15 ℃ to about 50 ℃. The method further includes heating the conversion product to remove the organic peroxide.
Description
Background
Technical Field
Embodiments of the present disclosure generally relate to methods of converting disulfides to conversion products and methods of producing cysteines.
Background
Cysteine, also known as 3-sulfo-L-alanine, is of the formula HO 3 SCH 2 CH(NH 2 )CO 2 Organic compounds of H. Cysteine is a non-toxic, non-allergenic physiological compound present in, for example, platelets and leukocytes of human and animal blood. Cysteine has a number of applications including pharmaceutical and water purification applications. For example, cysteine is useful in the treatment of ichthyosis, body odor, hangover and dermatological disorders (such as dandruff, acne, psoriasis, hyperkeratosis palmaris, hyperkeratosis plantaris and keratinization disorders). Traditional methods of prevention and treatment for alleviating the dermatological symptoms of keratinization disorders typically involve topical application of solutions, gels, emulsions, creams, ointments, sticks, powders or sprays containing cysteine. In water purification applications, cysteine functionalized membranes exhibit excellent performance in oil/water separation and removal of bacteria from contaminated water without significant scaling or reduction in membrane flux.
However, the production cost of manufacturing cysteine is high (about $200/kg) compared to cystine (about $30/kg) which is commonly used to synthesize cysteine. The high production costs are mainly due to the most advanced cysteine manufacturing methods. One conventional method of manufacturing cysteine is to oxidize cystine with bromine. The cost, safety and post-synthesis handling procedures of molecular bromine make this approach too time consuming and potentially dangerous. Another conventional method involves indirect electrooxidation from L-cystine using hydrobromic acid (HBr). However, in large scale, the in situ formation of bromine from HBr is dangerous. Other advanced methods of producing cysteine involve the use of chlorine-containing reagents such as t-butyl hypochlorite. However, this oxidizer is costly and dangerous in large scale cases because of the decomposition of t-butyl hypochlorite in water followed by the generation of chlorine. Electrochemical methods for producing cysteine are also known, but are generally impractical for large scale commercial applications. These known processes are inefficient, require large amounts of oxidizing agents, are not available for large-scale production, produce hazardous materials, and are too costly. However, oxidation of cystine is not the only one, as other compounds having disulfide bonds are oxidized to useful materials by known methods, which is costly, inefficient, and potentially dangerous.
There is a need for new and improved methods of oxidizing compounds having disulfide bonds that overcome one or more of the above-described drawbacks.
Disclosure of Invention
Embodiments of the present disclosure generally relate to methods of converting disulfides to conversion products and methods of producing cysteines.
In one embodiment, a method of converting cystine to a conversion product is provided. The method includes introducing an organic peroxide and water into cystine to form a mixture. The method further comprises reacting the mixture under conversion conditions to form a conversion product, wherein the conversion product comprises cysteine, the amount of cysteine in the conversion product is greater than about 90wt% based on the total weight of the conversion product, and the conversion conditions comprise a conversion temperature of about 15 ℃ to about 50 ℃. The method further includes heating the conversion product to remove the organic peroxide.
In another embodiment, a method of converting an organic disulfide to a conversion product is provided. The method includes introducing an organic peroxide into an organic disulfide to form a mixture, the organic disulfide having the formula R 1 -S-S-R 2 Wherein R is 1 And R is 2 Each independently is C 1 -C 20 Unsubstituted hydrocarbon radical or C 1 -C 20 Substituted hydrocarbyl groups. The method further comprises reacting the mixture under conversion conditions to form a conversion product, wherein the conversion product comprises sulfonic acid and is based on the total of the conversion productsThe amount of sulfonic acid in the conversion product is greater than about 90wt% by weight. The method further comprises removing the organic peroxide by heating the conversion product, exposing the conversion product to a pressure of less than about 1atm, or both.
In another embodiment, a method of converting an organic disulfide to a conversion product is provided. The method comprises introducing an organic peroxide comprising performic acid, peracetic acid, or a combination thereof, into an organic disulfide having the formula R to form a mixture 1 -S-S-R 2 Wherein R is 1 And R is 2 Each independently is C 1 -C 20 Unsubstituted hydrocarbon radical or C 1 -C 20 Substituted hydrocarbyl groups. The method further comprises reacting the mixture under conversion conditions to form a conversion product, wherein the conversion product comprises sulfonic acid, and the amount of sulfonic acid in the conversion product is greater than about 90wt% based on the total weight of the conversion product. The method further comprises removing the organic peroxide by heating the conversion product, exposing the conversion product to a pressure of less than about 1atm, or both.
Drawings
So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only exemplary embodiments and are therefore not to be considered limiting of its scope, for the embodiments may admit to other equally effective embodiments.
Fig. 1 illustrates an example of a conversion reaction of an organic disulfide to a conversion product in accordance with at least one embodiment of the present disclosure.
Fig. 2 illustrates an example of a conversion reaction of cystine to a conversion product according to at least one embodiment of the present disclosure.
Fig. 3 shows exemplary proton nuclear magnetic resonance (1H NMR) spectra of products of comparative and example conversion processes according to at least one embodiment of the present disclosure.
The drawings included herein illustrate various embodiments of the disclosure. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.
Detailed Description
Embodiments of the present disclosure generally relate to methods of converting disulfides to conversion products and methods of producing cysteines. The present inventors have discovered a new and improved process for converting disulfides, such as compounds having disulfide bonds, into conversion products. Briefly, in some embodiments, an organic peroxide is used to convert a compound having disulfide bonds to a conversion product, e.g., one or more sulfonic acids. Excess reagents for the conversion reaction may be removed from the product or product mixture by, for example, evaporation. The methods described herein are efficient, inexpensive, can be performed on a commercially viable scale, and do not produce deleterious chemicals as compared to conventional methods of oxidizing disulfide-containing compounds. For example, in some embodiments, the methods described herein are capable of producing a desired product (e.g., cysteine from cystine) in greater than 90% yield, with high conversion and high purity. Such high purity and high yields are not observed by practicing conventional methods, which generally require extensive purification to obtain the desired product from the crude reaction mixture. Furthermore, the methods described herein show reduced complexity and significantly reduced reaction time as a function of yield, or yield increases in comparable reaction time relative to conventional methods. Furthermore, the embodiments described herein do not require solvent extraction operations and extensive processing procedures, and the starting materials do not require solid support.
The methods described herein relate to the production of conversion products, e.g., the production of sulfonic acids from organic disulfides. These methods generally include introducing an organic peroxide into an organic disulfide to form a mixture, and reacting the mixture under conversion conditions to form one or more conversion products. Fig. 1 shows a general reaction scheme for converting an organic disulfide 101 to exemplary conversion products 103 and 104 using an oxidizing agent 102 (e.g., an organic peroxide).
In some embodiments, the organic disulfide has formula R 1 -S-S-R 2 ，
Wherein the method comprises the steps of
R 1 And R is 2 Each independently is C 1 -C 100 Unsubstituted hydrocarbon group (e.g. C 1 -C 40 Unsubstituted hydrocarbon radicals, e.g. C 1 -C 20 Unsubstituted hydrocarbon radicals, e.g. C 1 -C 10 Unsubstituted hydrocarbon radicals, e.g. C 1 -C 6 Unsubstituted hydrocarbyl), C 1 -C 100 Substituted hydrocarbon radicals (e.g. C 1 -C 40 Substituted hydrocarbon radicals, e.g. C 1 -C 20 Substituted hydrocarbon radicals, e.g. C 1 -C 10 Substituted hydrocarbon radicals, e.g. C 1 -C 6 Substituted hydrocarbyl group), C 4 -C 100 Unsubstituted aryl (e.g. C 4 -C 40 Unsubstituted aryl groups, e.g. C 4 -C 20 Unsubstituted aryl groups, e.g. C 4 -C 10 Unsubstituted aryl), C 4 -C 100 Substituted aryl groups (e.g. C 4 -C 40 Substituted aryl groups, e.g. C 4 -C 20 Substituted aryl groups, e.g. C 4 -C 10 Substituted aryl), or R 1 And R is 2 Can be linked to form a saturated ring, an unsaturated ring, a substituted saturated ring, or a substituted unsaturated ring, e.g. substituted or unsubstituted C 2 To C 100 A cyclic ring or a polycyclic ring. R is R 1 And R is 2 May each independently be saturated or unsaturated, substituted or unsubstituted, linear or branched, cyclic or acyclic, aromatic or non-aromatic. R is R 1 And R is 2 May be the same or different.
In at least one embodiment, and when R 1 And/or R 2 In the case of substituted hydrocarbyl or substituted aryl groups, at least one carbon of the substituted hydrocarbyl or substituted aryl group has been substituted with at least one heteroatom or heteroatom-containing group, e.g., one or more elements of groups 13-17 of the periodic Table of the elements, e.g., halogen (F, cl, br or I), O, N, se, te,p, as, sb, S, B, si, ge, sn, pb, e.g. NR #) 2 OR (e.g. OH OR O) 2 H)、SeR*、TeR*、PR* 2 、AsR* 2 、SbR* 2 SR, SOx (where x=2 or 3), BR 2 、SiR* 3 、GeR* 3 、SnR* 3 、PbR* 3 Etc., or at least one heteroatom has been inserted into the hydrocarbon radical or the aromatic radical, e.g., halogen (Cl, br, I, F), O, N, S, se, te, NR, PR, asR, sbR, BR, siR 2 、GeR* 2 、SnR* 2 、PbR* 2 And the like, wherein R is independently hydrogen, hydrocarbyl (e.g., C 1 -C 10 ) Or two or more R may be linked together to form a substituted or unsubstituted fully saturated, partially unsaturated, fully unsaturated or aromatic cyclic or polycyclic structure.
The organic peroxide may have the following structure: r is R 3 -O-O-R 4 Wherein
R 3 Is C 1 -C 40 Unsubstituted hydrocarbon group (e.g. C 1 -C 20 Unsubstituted hydrocarbon radicals, e.g. C 1 -C 10 Unsubstituted hydrocarbon radicals, e.g. C 1 -C 6 Unsubstituted hydrocarbyl), C 1 -C 40 Substituted hydrocarbon radicals (e.g. C 1 -C 20 Substituted hydrocarbon radicals, e.g. C 1 -C 10 Substituted hydrocarbon radicals, e.g. C 1 -C 6 Substituted hydrocarbyl group), C 4 -C 100 Unsubstituted aryl (e.g. C 4 -C 40 Unsubstituted aryl groups, e.g. C 4 -C 20 Unsubstituted aryl groups, e.g. C 4 -C 10 Unsubstituted aryl), or C 4 -C 100 Substituted aryl groups (e.g. C 4 -C 40 Substituted aryl groups, e.g. C 4 -C 20 Substituted aryl groups, e.g. C 4 -C 10 Substituted aryl); and
R 4 is hydrogen, C 1 -C 40 Unsubstituted hydrocarbon group (e.g. C 1 -C 20 Unsubstituted hydrocarbon radicals, e.g. C 1 -C 10 Unsubstituted hydrocarbon radicals, e.g. C 1 -C 6 Unsubstituted hydrocarbyl), C 1 -C 40 Substituted hydrocarbon radicals (e.g. C 1 -C 20 Substituted hydrocarbon radicals, e.g. C 1 -C 10 Substituted hydrocarbon radicals, e.g. C 1 -C 6 Substituted hydrocarbyl group), C 4 -C 100 Unsubstituted aryl (e.g. C 4 -C 40 Unsubstituted aryl groups, e.g. C 4 -C 20 Unsubstituted aryl groups, e.g. C 4 -C 10 Unsubstituted aryl), or C 4 -C 100 Substituted aryl groups (e.g. C 4 -C 40 Substituted aryl groups, e.g. C 4 -C 20 Substituted aryl groups, e.g. C 4 -C 10 Substituted aryl).
In some embodiments, the organic acid is a percarboxylic acid (or peroxyacid) R 5 CO 3 H is derived from carboxylic acids R 5 CO 2 H and hydrogen peroxide. R is R 5 May include R as above 3 Or R is 4 Those listed as unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted aryl, and substituted aryl. In at least one embodiment, the organic peroxide is selected to have an oxidation potential greater than that of hydrogen peroxide, for example greater than-1.77V. R is R 3 And R is 4 May each independently be saturated or unsaturated, substituted or unsubstituted, linear or branched, cyclic or acyclic, aromatic or non-aromatic.
In some embodiments, the organic peroxide may be made from a mixture of hydrogen peroxide and an organic acid, e.g., a substituted or unsubstituted, branched or unbranched, cyclic or acyclic C 1 -C 40 Organic acid, C 1 -C 20 Organic acid, C 1 -C 10 Organic acids or C 1 -C 6 An organic acid. Illustrative, but non-limiting examples of organic acids include acetic acid, formic acid, benzoic acid, trifluoroacetic acid, propionic acid, and butyric acid. The hydrogen peroxide utilized may be in the form of an aqueous solution, for example, an aqueous solution of 50wt% or less, such as an aqueous solution of 30wt% or less. The organic peroxide is produced after the organic acid is introduced into the hydrogen peroxide. For example, introducing acetic acid into the peroxidationHydrogen will produce peracetic acid (CH) 3 CO 3 H) While the introduction of formic acid into hydrogen peroxide produces performic acid (CH 2 O 3 ). Excess organic acid with hydrogen peroxide or vice versa can be used to generate the organic peroxide.
Useful solvents for the conversion reaction may include water and/or alcohols such as isopropanol and ethanol. The water is introduced into the organic disulphide before, during and/or after the addition of the organic peroxide. In some embodiments, the organic peroxide is or includes an aqueous mixture having an organic peroxide concentration of about 5% v/v or greater, such as about 10% v/v to about 80% v/v, such as about 20% v/v to about 50% v/v, and such as about 30% v/v to about 40% v/v.
As a non-limiting example of the above conversion reaction, FIG. 2 shows the conversion of cystine to a conversion product. Wherein cystine (C) 6 H 12 N 2 O 4 S 2 ) 201 is converted to a polypeptide comprising cysteine (C 3 H 7 NO 5 S) 203. Oxidant 102 ([ O)]) Including those described above.
According to some embodiments, the conversion conditions of the conversion reaction may include temperature (e.g., conversion temperature) and time (e.g., conversion time). In some embodiments, the conversion temperature is from about 0 ℃ to about 80 ℃, such as from about 5 ℃ to about 75 ℃, such as from about 10 ℃ to about 70 ℃, such as from about 15 ℃ to about 65 ℃, such as from about 20 ℃ to about 60 ℃, such as from about 25 ℃ to about 55 ℃, such as from about 30 ℃ to about 50 ℃, such as from about 35 ℃ to about 45 ℃, such as from about 40 ℃ to about 45 ℃. In at least one embodiment, the conversion temperature may be from about 15 ℃ to about 25 ℃. In some embodiments, the conversion temperature is T1 to T2, wherein T1 and T2 (in degrees celsius) are 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95, respectively, so long as T2> T1. The conversion time of the conversion conditions may be at least about 1 minute (min) and/or less than about 48 hours (h), for example from about 30 minutes to about 10 hours, such as from about 1 hour to about 5 hours, such as from about 2 hours to about 4 hours.
In some embodiments, the transformation condition packageIncluding stirring, mixing, and/or otherwise agitating the reaction mixture to ensure uniformity of the reaction mixture. The conversion conditions may also include the presence of a non-reactive gas (e.g., N 2 And/or Ar) to carry out the conversion reaction. Any reasonable pressure may be used during the conversion reaction. In one embodiment, the conversion is carried out at or about atmospheric pressure, however, it is contemplated that the conversion may be carried out at higher or lower pressures. In at least one embodiment, the reaction mixture is free or substantially free of halides, such as bromine.
After conversion for an appropriate reaction time, the conversion product from the conversion reaction may comprise one or more desired products (e.g., sulfonic acid), as well as other materials, such as organic acids, hydrogen peroxide, and/or organic peroxides. According to some embodiments, one or more of these materials is removed from the conversion product under removal conditions. The removal conditions may include heating the conversion product to a temperature of about 110 ℃ or less, such as about 100 ℃ or less, such as about 90 ℃ or less, such as about 30 ℃ to about 70 ℃, such as about 40 ℃ to about 50 ℃, or about 60 ℃ to about 70 ℃. Any reasonable pressure may be used to aid in the removal of organic acids, hydrogen peroxide, organic peroxides, and/or other substances. In one embodiment, the removal of material is performed at or about atmospheric pressure, however, it is contemplated that the removal of material may be performed at higher or lower pressures. Thus, excess reagent may be removed by evaporation.
In at least one embodiment, the molar ratio of acid (e.g., organic acid) to hydrogen peroxide in the conversion reaction is from about 3:1 to about 1:3, such as from about 2:1 to about 1:2, such as from about 1.5:1 to about 1:1.5.
In at least one embodiment, the molar ratio of organic acid to organic disulfide in the conversion reaction is from about 20:1 to about 1:1, such as from about 15:1 to about 2:1, such as from about 12:1 to about 4:1.
The conversion reaction produces a conversion product that includes a sulfonic acid (e.g., cysteine). The amount of sulfonic acid in the conversion product is about 75wt% or more, such as about 80wt% or more, such as about 85wt% or more, such as about 90wt% or more, such as about 95wt% or more, such as about 99wt% or more, such as about 100wt% based on the total weight of the conversion product.
In the conversion reaction, the conversion of the organic disulfide to the conversion product (e.g., cysteine) may be about 50% or greater, such as about 60% or greater, such as about 70% or greater, such as about 75% or greater, such as about 80% or greater, such as about 85% or greater, such as about 90% or greater, such as about 95% or greater, such as about 99% or greater, such as about 100% based on the amount of organic disulfide used in the conversion product.
For the process for producing the conversion product (e.g., sulfonic acid), the molar ratio of acid (e.g., organic acid) to hydrogen peroxide, the molar ratio of hydrogen peroxide to organic disulfide, the molar ratio of acid to organic disulfide, and the molar ratio of organic peroxide to organic disulfide are determined based on the molar ratio of starting materials used for the conversion reaction.
In contrast to conventional methods of producing cysteine, the methods described herein are practical, inexpensive, for example, for large-scale commercial applications, and do not involve the use or creation of hazardous materials.
The following illustrative examples are not intended to limit the scope of the embodiments of the present disclosure.
Examples
Cystine, glacial acetic acid (CH) 3 CO 2 H) Nitric acid (HNO) 3 ) Formic acid (HCO) 2 H) And hydrogen peroxide solutions are commercially available. Using a proper amount of D 2 O was used as a deuterated solvent, and the reaction products (e.g., conversion products) of the following examples and comparative examples were analyzed for coarse materials by 1H NMR at 500 MHz. The 1H NMR spectra of the examples and comparative examples and the 1H NMR spectra of commercially available cysteines are shown in FIG. 3.
Example 1: cystine powder (about 0.1 g) was stirred at about 25℃for 4 hours, dissolved in glacial acetic acid (about 30 mL) and about 20mL H 2 O 2 (30% (w/w) in water). Slowly evaporating the excess peracetic acid by stirring on a hot plate at about 40 ℃ to about 45 ℃ and passing 1 The residue was analyzed by H NMR. Residues of 1 The H NMR spectrum is shown in fig. 3 as ex.1. Yield of L-cysteineIs that>Percent conversion of 99%, cystine was determined as>99%. The results show that L-cysteine is produced in high purity and in high yield.
Example 2: cystine powder (0.1 g) was dissolved in a mixture of formic acid (98%, 36 mL) and about 5mL hydrogen peroxide (30% (w/w) in water). The mixture was stirred at about 25 ℃ for about 2.5 hours. Stirring on a hot plate at about 40deg.C to about 45deg.C, slowly evaporating excessive performic acid, using 1 The residue was analyzed by H NMR. Residues of 1 HNMR spectra are shown as ex.2 in fig. 3. The yield of L-cysteine was>Percent conversion of 99%, cystine was determined as>99%. The results show that L-cysteine is produced in high purity and in high yield.
Comparative example 1: cystine powder (0.1 g) was added to water (10 mL). Adding HNO to the mixture 3 (70%, 2 mL) and the resulting mixture was stirred at about 25℃for 30 minutes. The mixture was stirred on a hot plate at 80℃and the excess water and HNO evaporated 3 Until dry. The resulting powder was redissolved in a minimum amount of water and evaporated again. The yield of L-cysteine was 0% and the percent conversion of cystine was 100%. Residues of 1 The H NMR spectrum is shown as c.ex.1 in fig. 3. Here, no cysteine is produced, as 1 Additional peaks and broadened peaks in the H NMR spectrum.
Comparative example 2: cystine powder (0.1 g) was dispersed in 20mL H 2 O 2 (30% (w/w) in water). The mixture was stirred at 80 ℃ for 30 minutes until the solution became clear. The mixture was stirred on a hot plate at 80℃and excess water and hydrogen peroxide were evaporated. Residues of 1 The H NMR spectrum is shown as c.ex.2 in fig. 3. The yield of L-cysteine was about 69%, and the percent conversion of cystine was determined as>98%. Here, although some cysteines are formed, the product residues contain a large amount of impurities, such as 1 Additional peaks and broadened peaks in the H NMR spectrum are shown. Furthermore, in contrast to the examples described herein, performing the procedure of comparative examples 1 and 2 can be challenging because, for example, maintaining the temperature at 80 ℃ is unsafe becauseThe reaction is highly exothermic.
Overall, the results show that high purity cysteine can be produced at, for example, low temperature, short reaction time and complete conversion of the starting material cystine. The methods described herein are practical for large scale commercial applications, do not involve or produce hazardous materials, and are inexpensive compared to conventional methods of producing cysteine.
Embodiments described herein enable efficient conversion of, for example, organic disulfides to conversion products. As an example, the inventors have discovered a new and improved process for producing cysteine by reacting cystine with an organic peroxide. The method can obtain high-purity cysteine in high yield. In addition, excess reagent may be removed by heating or subjecting the conversion product to reduced pressure.
List of embodiments
The present disclosure provides, inter alia, the following aspects, each of which may be considered to optionally include any alternative aspect:
clause 1. A method of converting cystine to a conversion product comprising:
introducing an organic peroxide and water into cystine to form a mixture;
reacting the mixture under conversion conditions to form the conversion product, wherein
The conversion product comprises cysteine;
the amount of cysteine in the conversion product is greater than about 90wt% based on the total weight of the conversion product; and
the conversion conditions include a temperature of about 15 ℃ to about 50 ℃; and
the conversion product is heated to remove any residual organic peroxide.
Clause 2. The method of clause 1, wherein the amount of cysteine in the conversion product is greater than about 95 weight percent based on the total weight of the conversion product.
Clause 3 the method of clause 1 or clause 2, wherein heating the conversion product to remove the organic peroxide comprises heating the conversion product to a temperature of about 80 ℃ or less.
Clause 4. The method of clause 3, wherein the conversion temperature is about 40 ℃ to about 50 ℃.
Clause 5 the method of any of clauses 1-4, wherein the conversion of cystine to cysteine is about 95% or more.
The method of any of clauses 1-5, wherein the organic peroxide has an oxidation potential greater than about 1.77V.
Clause 7. The method of any of clauses 1-6, wherein the organic peroxide is formed by introducing an organic acid into hydrogen peroxide.
Clause 8. The method of clause 7, wherein the organic peroxide is an aqueous solution having a concentration of about 10% v/v to about 80% v/v.
The method of any of clauses 1-8, wherein the organic peroxide comprises performic acid, peracetic acid, or a combination thereof.
Clause 10. A method of converting an organic disulfide into a conversion product comprising
Introducing an organic peroxide into an organic disulfide to form a mixture, the organic disulfide having the formula R 1 -S-S-R 2 Wherein R is 1 And R is 2 Each independently is C 1 -C 20 Unsubstituted hydrocarbon radical or C 1 -C 20 A substituted hydrocarbyl group;
reacting the mixture under conversion conditions to form the conversion product, wherein
The conversion product comprises a sulfonic acid; and is also provided with
The amount of sulfonic acid in the conversion product is greater than about 90wt%, based on the total weight of the conversion product; and
the organic peroxide is removed by heating the conversion product, exposing the conversion product to a pressure of less than about 1atm, or both.
Clause 11. The method of clause 10, wherein the conversion conditions comprise a temperature of from about 0 ℃ to about 80 ℃.
Clause 12 the method of clause 10 or clause 11, wherein the transformation conditions comprise about 10 hours or less.
Clause 13 the method of any of clauses 10-12, wherein R 1 And R is 2 Are identical.
The method of any of clauses 10-13, wherein the amount of sulfonic acid in the conversion product is greater than about 95 weight percent based on the total weight of the conversion product.
The method of any of clauses 10-14, wherein removing the organic peroxide by heating the conversion product comprises heating the conversion product to a temperature of about 80 ℃ or less.
Clause 16. A method of converting an organic disulfide into a conversion product comprising
Introducing an organic peroxide comprising performic acid, peracetic acid, or a combination thereof into an organic disulfide having the formula R to form a mixture 1 -S-S-R 2 Wherein R is 1 And R is 2 Each independently is C 1 -C 20 Unsubstituted hydrocarbon radical or C 1 -C 20 A substituted hydrocarbyl group;
reacting the mixture under conversion conditions to form a conversion product, wherein
The conversion product comprises a sulfonic acid; and is also provided with
The amount of sulfonic acid in the conversion product is greater than about 90wt%, based on the total weight of the conversion product; and
the organic peroxide is removed by heating the conversion product, exposing the conversion product to a pressure of less than about 1atm, or both.
The method of clause 17, wherein the conversion conditions comprise a temperature of about 15 ℃ to about 50 ℃.
The method of clause 16 or clause 17, wherein removing the organic peroxide by heating the conversion product comprises heating the conversion product to a temperature of about 40 ℃ to about 50 ℃.
Clause 19 the method of any of clauses 16-19, wherein R 1 And R is 2 Are identical.
The method of any of clauses 16-19, wherein the amount of sulfonic acid in the conversion product is greater than about 95 weight percent based on the total weight of the conversion product.
In the foregoing, embodiments of the present disclosure are mentioned. However, it should be understood that the present disclosure is not limited to the specifically described embodiments. Rather, any combination of the following features and elements, whether related to different embodiments or not, is contemplated to implement and practice the present disclosure. Furthermore, although embodiments of the disclosure may achieve advantages over other possible solutions and/or over the prior art, whether an embodiment achieves a particular advantage is not limiting of the disclosure. Thus, the foregoing aspects, features, embodiments and advantages are merely illustrative and are not to be considered elements or limitations of the appended claims except as explicitly mentioned in the claims. Likewise, references to "the present disclosure" should not be construed as an generalization of any inventive subject matter disclosed herein, nor should it be considered an element or limitation of the appended claims except where explicitly recited in a claim.
As used herein, unless otherwise specified, the term "C n "refers to hydrocarbons having n carbon atoms per molecule, where n is a positive integer. The term "hydrocarbon" refers to a class of compounds containing hydrogen bonded to carbon and includes (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of (saturated and/or unsaturated) hydrocarbon compounds, including mixtures of hydrocarbon compounds having different n values. Similarly, "C m -C y "group or compound" refers to a group or compound having a total number of carbon atoms in the range of m to y. Thus C 1 -C 50 Alkyl refers to alkyl groups having a total number of carbon atoms in the range of 1 to 50.
For the purposes of this disclosure, unless otherwise indicated, the terms "hydrocarbon radical", "hydrocarbyl group" or "hydrocarbyl group" interchangeably refer to a group consisting of only hydrogen atoms and carbon atoms. The hydrocarbyl group may be saturated or unsaturated, linear or branched, cyclic or acyclic, aromatic or non-aromatic. For the purposes of this disclosure, the term "aryl" or "aryl group" interchangeably refers to a hydrocarbon group comprising an aromatic ring structure therein, unless otherwise specified.
Unless otherwise indicated, chemical fragments of the application may be substituted or unsubstituted. For the purposes of this disclosure, unless otherwise indicated, substituted hydrocarbyl and substituted aryl refer to hydrocarbyl and aryl, respectively, wherein at least one hydrogen atom has been substituted with a heteroatom or heteroatom-containing group, e.g., with at least one functional group, such as one or more elements from groups 13-17 of the periodic table of elements, e.g., halogen (F, cl, br, or I), O, N, se, te, P, as, sb, S, B, si, ge, sn, pb, etc., e.g., NR 2 OR is (e.g. OH OR O 2 H)、SeR*、TeR*、PR* 2 、AsR* 2 、SbR* 2 、SR*、SO x (where x=2 or 3), BR 2 、SiR* 3 、GeR* 3 、SnR* 3 、PbR* 3 Or the like, or wherein at least one heteroatom has been inserted into the hydrocarbyl or aryl group, such as halogen (F, cl, br or I), O, S, se, te, NR, PR, asR, sbR, BR, siR 2 、GeR* 2 、SnR* 2 、PbR* 2 One or more of the groups, wherein R is independently hydrogen, hydrocarbyl (e.g., C 1 -C 10 ) Or two or more R may join together to form a substituted or unsubstituted fully saturated, partially unsaturated, fully unsaturated, or aromatic or polycyclic structure. For example, at least one hydrogen may be substituted with an oxygen-containing group, such as a carboxyl group or a carbonyl group.
As another example, if there is an isomer of the named group of molecules (e.g., L-cysteine), reference to one member of the group (e.g., L-cysteine) should explicitly disclose the remaining isomers in the family (e.g., R-cysteine). Likewise, reference to a named molecule without specifying a particular isomer (e.g., cysteine) should explicitly disclose all isomers (e.g., L-cysteine and R-cysteine).
For the purposes of this disclosure, unless otherwise indicated, all numbers within the specification and claims herein are modified by the use of "about" or "approximately" indicated values and take into account experimental errors and variations that would be expected by one of ordinary skill in the art. For brevity, only certain ranges are explicitly disclosed herein. However, a range from any lower limit may be combined with any upper limit to list a range not explicitly recited, and a range from any lower limit may be combined with any other lower limit to list a range not explicitly recited, in the same manner, a range from any upper limit may be combined with any other upper limit to list a range not explicitly recited. Furthermore, each point or individual value between its endpoints is included within a certain range even if not explicitly recited. Thus, each point or individual value may be combined as its own lower or upper limit with any other point or individual value or any other lower or upper limit to list ranges not explicitly recited.
As used herein, the indefinite article "a" or "an" shall mean "at least one" unless otherwise indicated or clearly indicated by context. For example, an aspect that includes "a monomer" includes an aspect that includes one, two, or more monomers, unless the contrary specification or context clearly indicates that only one monomer is included.
While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (15)
1. A method of converting cystine to a conversion product comprising:
introducing an organic peroxide and water into cystine to form a mixture;
reacting the mixture under conversion conditions to form a conversion product, wherein
The conversion product comprises cysteine;
the amount of cysteine in the conversion product is greater than about 90wt% based on the total weight of the conversion product; and
the conversion conditions include a temperature of about 15 ℃ to about 50 ℃; and
heating the conversion product to remove the organic peroxide.
2. The method according to claim 1, wherein the amount of cysteine in the conversion product is greater than about 95wt% based on the total weight of the conversion product.
3. The method of claim 1, wherein heating the conversion product to remove organic peroxide comprises heating the conversion product to a temperature of about 80 ℃ or less.
4. A process according to claim 3 wherein the conversion temperature is from about 40 ℃ to about 50 ℃.
5. The method according to claim 1, wherein the conversion of cystine to cysteine is about 95% or greater.
6. The method of claim 1, wherein the oxidation potential of the organic peroxide is greater than about 1.77V.
7. The method of claim 1, wherein the organic peroxide is formed by introducing an organic acid into hydrogen peroxide.
8. The method of claim 7 wherein the organic peroxide is an aqueous solution having a concentration of organic peroxide of from about 10% v/v to about 80% v/v.
9. The method of claim 1, wherein the organic peroxide comprises performic acid, peracetic acid, or a combination thereof.
10. A process for converting an organic disulfide into a conversion product comprising
Introducing an organic peroxide into an organic disulfide to form a mixture, the organic disulfide having the formula R 1 -S-S-R 2 Wherein R is 1 And R is 2 Each independently is C 1 -C 20 Unsubstituted hydrocarbon radical or C 1 -C 20 A substituted hydrocarbyl group;
reacting the mixture under conversion conditions to form a conversion product, wherein
The conversion product comprises a sulfonic acid; and is also provided with
The amount of sulfonic acid in the conversion product is greater than about 90wt%, based on the total weight of the conversion product; and
the organic peroxide is removed by heating the conversion product, exposing the conversion product to a pressure of less than about 1atm, or both.
11. The method according to claim 10, wherein
The conversion conditions include a temperature of from about 0 ℃ to about 80 ℃;
the conversion conditions include a time of about 10 hours or less;
R 1 and R is 2 Are identical; and is also provided with
The amount of sulfonic acid in the conversion product is greater than about 95 weight percent based on the total weight of the conversion product.
12. The method of claim 10, wherein removing the organic peroxide by heating the conversion product comprises heating the conversion product to a temperature of about 80 ℃ or less.
13. A process for converting an organic disulfide into a conversion product comprising
Introducing an organic peroxide comprising performic acid, peracetic acid, or a combination thereof into an organic disulfide having the formula R to form a mixture 1 -S-S-R 2 Wherein R is 1 And R is 2 Each independently is C 1 -C 20 Unsubstituted hydrocarbon radical or C 1 -C 20 A substituted hydrocarbyl group;
reacting the mixture under conversion conditions to form a conversion product, wherein
The conversion product comprises a sulfonic acid; and is also provided with
The amount of sulfonic acid in the conversion product is greater than about 90wt%, based on the total weight of the conversion product; and
the organic peroxide is removed by heating the conversion product, exposing the conversion product to a pressure of less than about 1atm, or both.
14. The method according to claim 13, wherein
The conversion conditions include a temperature of about 15 ℃ to about 50 ℃; and
removing the organic peroxide by heating the conversion product includes heating the conversion product to a temperature of about 40 ℃ to about 50 ℃.
15. The method according to claim 13, wherein R 1 And R is 2 Are identical.
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| US63/090,739 | 2020-10-13 | ||
| US17/319,921 US11401239B1 (en) | 2020-10-13 | 2021-05-13 | Process for converting disulfides to conversion products and process for producing cysteic acid |
| US17/319,921 | 2021-05-13 | ||
| PCT/IB2021/059344 WO2022079595A1 (en) | 2020-10-13 | 2021-10-12 | Process for converting disulfides to conversion products and process for producing cysteic acid |
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