Method for preparing sulfamic acid derivative
A reaction of urea derivatives with fluorosulfonic or chlorosulfonic acid produces sulfamic acid derivatives with high purity and yield, addressing the inefficiencies of previous methods by eliminating toxic gases and enabling cost-effective commercial production.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- CHUN BO LTD
- Filing Date
- 2025-11-12
- Publication Date
- 2026-05-21
AI Technical Summary
Existing methods for producing sulfamic acid derivatives, such as those described in Korean Patent Publications 10-2019-0072566, 10-2019-0075042, and 10-2023-0054416, require toxic gases like SO2F2 or SO2FCl, leading to low purity, low yield, and economic inefficiencies, making large-scale commercial production difficult.
A method involving the reaction of a urea derivative with fluorosulfonic acid or chlorosulfonic acid under solvent-free or solvent conditions, without using toxic gases, to produce sulfamic acid derivatives with high purity and yield, enabling commercial mass production.
The method achieves high-purity sulfamic acid derivatives with high yield and minimal side reactions, facilitating cost-effective commercial production by avoiding the use of expensive reagents like SuFEx.
Smart Images
Figure PCTKR2025095715-APPB-IMG-000001 
Figure PCTKR2025095715-APPB-IMG-000002 
Figure PCTKR2025095715-APPB-IMG-000003
Abstract
Description
Method for preparing sulfamic acid derivatives
[0001] The present invention relates to a method for producing a derivative of sulfamic acid. Specifically, it relates to a method for producing a halogenated sulfamic acid derivative.
[0002] The sulfamic acid derivative of Chemical Formula 1 below is a substance used as a solvent or additive in battery electrolytes.
[0003] Chemical formula 1
[0004]
[0005] In the above formula,
[0006] R1 is F or Cl and
[0007] R2 and R3 are each independently a substituted or unsubstituted linear or branched C1-C24 alkyl group, a substituted or unsubstituted linear or branched C2-C24 alkenyl group, a substituted or unsubstituted C6-C10 aryl group or a substituted or unsubstituted C5-C10 heteroaryl group, and
[0008] R2 and R3 can combine to form a ring that may or may not contain additional heteroatoms.
[0009] There are reports that when a sulfamic acid derivative of Chemical Formula 1 is used in the electrolyte of a battery, it inhibits corrosion of aluminum current collectors by lithium bis(trifluoromethanesulfonyl)imide.
[0010] As a method for preparing a sulfamic acid derivative of Chemical Formula 1, Korean Published Patent Application 10-2019-0072566 disclosed a method using R2NH, sulfur trioxide, and a tertiary amine. Korean Published Patent Application 10-2019-0075042 disclosed a method for preparing a sulfamic acid derivative using an amine compound with SO2F2 or SO2FCl, etc. Korean Published Patent Application 10-2023-0054416 disclosed a method for preparing a fluorosulfamic acid derivative by performing a fluorine substitution reaction using a chlorosulfamic acid derivative.
[0011] However, the methods of Korean Patent Publication No. 10-2019-0072566 and Korean Patent Publication No. 10-2019-0075042 require the use of toxic gases such as SO3, SO2F2, or SO2FCl for the production of sulfamic acid derivatives, making it difficult to expect mass production through the above process. The method of producing fluorosulfamic acid from chlorosulfamic acid according to Korean Patent Publication No. 10-2023-0054416 has the disadvantage of being uneconomical due to low purity and low yield. Therefore, it is not possible to commercially produce the sulfamic acid derivative of Formula 1 in large quantities through the above methods.
[0012] In addition, there is a method of introducing SO2F functional groups to nitrogen (N) using SuFEx-IT of Chemical Formula 2 below, but SuFEx-IT is expensive, so it is difficult to use in mass production.
[0013] Chemical formula 2
[0014]
[0015] Accordingly, the objective of the present invention is to provide a method for producing a sulfamic acid derivative of Formula 1 that can be produced with high purity and high yield without using toxic gases such as SO2F2 or SO2FCl, and in particular, enables commercial mass production by not using expensive reagents.
[0016] To achieve the above objective, the present invention provides a method for preparing a sulfamic acid derivative of the following formula 1, characterized by reacting a urea derivative of the following formula 3 with a fluorosulfonic acid or chlorosulfonic acid.
[0017] Chemical formula 1
[0018]
[0019] Chemical formula 3
[0020] R2R3N-C(=O)-NR2R3
[0021] In the above formula,
[0022] R1 is F or Cl and
[0023] R2 and R3 are each independently a substituted or unsubstituted linear or branched C1-C24 alkyl group, a substituted or unsubstituted linear or branched C2-C24 alkenyl group, a substituted or unsubstituted C6-C10 aryl group or a substituted or unsubstituted C5-C10 heteroaryl group, and
[0024] R2 and R3 can combine to form a ring that may or may not contain additional heteroatoms.
[0025] The method for manufacturing sulfamic acid derivatives according to the present invention does not use toxic gases such as SO2F2 or SO2FCl, and has the effect of enabling the production of sulfamic acid derivatives with high purity and high yield due to minimal side reactions, and enables commercial mass production by not using the expensive reagent known as SuFEx.
[0026] The present invention will be described in detail below. Terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, and should be interpreted in a meaning and concept consistent with the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.
[0027] The present invention relates to a method for preparing a sulfamic acid derivative of Formula 1, characterized by reacting a urea derivative of Formula 3 with fluorosulfonic acid or chlorosulfonic acid.
[0028] Chemical formula 1
[0029]
[0030] Chemical formula 3
[0031] R2R3N-C(=O)-NR2R3
[0032] In the above formula,
[0033] R1 is F or Cl and
[0034] R2 and R3 are each independently a substituted or unsubstituted linear or branched C1-C24 alkyl group, a substituted or unsubstituted linear or branched C2-C24 alkenyl group, a substituted or unsubstituted C6-C10 aryl group or a substituted or unsubstituted C5-C10 heteroaryl group, and
[0035] R2 and R3 can combine to form a ring that may or may not contain additional heteroatoms.
[0036] In the above chemical formula, the heteroatom can be O, N, or S.
[0037] In the above chemical formula 1, R1 is preferably F.
[0038] In the above chemical formula 1, the substituents of R2 and R3 are halogens, OH, C1-C5 carbonyl groups, or alcohol groups, and preferably halogens.
[0039] In the above chemical formula 1, R2 and R3 are preferably the same.
[0040] In the above chemical formula 1, R2 and R3 are preferably C1-C10 alkyl, more preferably C1-C5 alkyl, and even more preferably methyl or ethyl.
[0041]
[0042] A method for preparing a sulfamic acid derivative of Formula 1 by reacting a urea derivative of Formula 3 with fluorosulfonic acid or chlorosulfonic acid is schematically illustrated as Reaction Scheme 1 below, with the case where R1 is F and R2 and R3 are methyl, but the reaction of the present invention is not limited thereto.
[0043] Reaction Equation 1
[0044]
[0045] The manufacturing method of the present invention will be described in detail below.
[0046] The reaction between the urea derivative of Formula 3 of the present invention and fluorosulfonic acid or chlorosulfonic acid can be carried out under a solvent or without a separate solvent. When the reaction is carried out under solvent-free conditions, there is no need to remove the solvent after the reaction, so there are advantages that are commercially and economically favorable, such as simple post-processing and no unnecessary waste generation.
[0047] When the reaction proceeds under a solvent, the solvent is preferably one that can effectively dissolve the reactants, particularly the urea derivative of Formula 3, and reduce side reactions, and is preferably one that is water-free and also free of carbonyl groups. Examples of solvents that can be used include toluene, benzene, acetonitrile, methylene chloride, 1,2-dichlorobenzene, etc.
[0048] At this time, the reaction can be carried out under an inert gas, preferably nitrogen gas.
[0049] The reaction between the urea derivative of Formula 3 and fluorosulfonic acid or chlorosulfonic acid is carried out under an inert gas atmosphere, in solvent or solvent-free conditions, by mixing the urea derivative of Formula 3 and the fluorosulfonic acid or chlorosulfonic acid and then stirring the mixture. The reaction temperature is 100°C to 160°C, preferably 100°C to 150°C. If the reaction temperature is below 100°C, the reaction between the urea derivative and the fluorosulfonic acid or chlorosulfonic acid does not proceed sufficiently. While increasing the reaction temperature can shorten the reaction time, if it exceeds 160°C, the effect of shortening the reaction time is not significant, there is a high possibility of side reactions occurring, and there is also a disadvantage that energy is required for heating, making it unfavorable for commercial production.
[0050] In the reaction between the urea derivative of the present invention and fluorosulfonic acid or chlorosulfonic acid, carbon dioxide is produced along with the sulfamic acid derivative, and the carbon dioxide can be removed as a gas during the reaction.
[0051] The reaction between a urea derivative and fluorosulfonic acid or chlorosulfonic acid can be carried out for 1 to 7 hours under sufficient stirring of the mixture. In this case, sulfamic acid derivatives can be produced with high yield and high purity without wasting energy.
[0052] The reaction between a urea derivative of Formula 3 and a fluorosulfonic acid or chlorosulfonic acid can be carried out by reacting 2 to 6 equivalents, preferably 2 to 5 equivalents, more preferably more than 2 to 5 equivalents, and even more preferably 2.1 to 5 equivalents, of fluorosulfonic acid or chlorosulfonic acid with respect to 1 equivalent of the urea derivative. When reacting 2 equivalents of fluorosulfonic acid or chlorosulfonic acid with respect to 1 equivalent of the urea derivative, there is an advantage in that the sulfamic acid derivative can be produced economically without wasting reactants. On the other hand, when reacting 1 equivalent of the urea derivative with an excess of fluorosulfonic acid or chlorosulfonic acid with an excess of more than 2 equivalents, there is an advantage in that the sulfamic acid derivative can be produced with higher purity and higher yield.
[0053] The sulfamic acid derivative of the present invention can be obtained by vacuum distillation after being prepared under solvent-free conditions.
[0054] The sulfamic acid derivative of the present invention can be obtained by preparing it using a solvent, removing the solvent under reduced pressure conditions, and then performing reduced pressure distillation.
[0055] The reduced pressure conditions may vary depending on the functional group of the compound of Formula 1 and the temperature, and may be less than 760 torr, 500 torr or less, 300 torr or less, or 100 torr or less.
[0056] The method for producing a sulfamic acid derivative of the present invention has the advantage of being able to obtain a sulfamic acid derivative with high yield and high purity by reacting a urea derivative with fluorosulfonic acid or chlorosulfonic acid under relatively mild conditions.
[0057] The present invention may additionally include a purification step to increase the purity of the manufactured sulfamic acid derivative.
[0058] The above purification step can obtain a higher purity sulfamic acid derivative by, for example, dissolving a sulfamic acid derivative obtained by reacting a urea derivative with fluorosulfonic acid or chlorosulfonic acid in a solvent and then filtering out insoluble components, or by removing the solvent from the filtrate by vacuum distillation without a filtration step.
[0059] As another example of the purification step, a sulfamic acid derivative obtained by reacting a urea derivative with fluorosulfonic acid or chlorosulfonic acid is dissolved in a solvent, and then the solution is either filtered or washed directly with purified water or alkaline water without filtration, and the solvent is removed by vacuum distillation to obtain a sulfamic acid derivative of higher purity. By washing with alkaline water, acidic components such as HF that may be generated as byproducts are removed, thereby enabling the production of a sulfamic acid derivative of higher purity.
[0060] The solvent used for purifying the above sulfamic acid derivative can be used without limitation as long as it is a solvent that can dissolve the sulfamic acid derivative and is easy to remove by vacuum distillation, preferably toluene, benzene, acetonitrile, methylene chloride, 1,2-dichlorobenzene, etc.
[0061] The solvent used in the above purification can be used in an amount of 100 to 300 parts by weight per 100 parts by weight of the urea derivative. When the solvent is used in the above amount, the sulfamic acid derivative can be obtained with high purity, and the use of unnecessary solvents is prevented, which has the advantage of making the sulfamic acid derivative economically.
[0062] Preferred embodiments of the present invention will be described in detail below. However, in describing the present invention, descriptions of already known conditions or configurations will be omitted to clarify the gist of the invention. Furthermore, the present invention is not limited to the following embodiments.
[0063] Example 1
[0064] 172.3 g (2 eq) of fluorosulfonic acid and 100.0 g (1 eq) of tetramethylurea were mixed in a 250 mL round-bottom flask equipped with a condenser and a magnetic stirring bar, and the mixture was heated and stirred at 110 °C for 4 hours under a dry nitrogen atmosphere. The mixture was cooled, and the spectrum of the sample was analyzed by nuclear magnetic resonance analysis.
[0065] The completion of the reaction was confirmed through the aforementioned nuclear magnetic resonance analysis, and the obtained crude product was purified through vacuum distillation.
[0066] Yield: 70%, Purity 99.5%
[0067] Example 2
[0068] 172.3 g (2 eq) of fluorosulfonic acid and 100.0 g (1 eq) of tetramethylurea were mixed in a 250 mL round-bottom flask equipped with a condenser and a magnetic stirring bar, and the mixture was heated and stirred at 110 °C for 4 hours under a dry nitrogen atmosphere. The mixture was cooled, and the spectrum of the sample was analyzed by nuclear magnetic resonance analysis.
[0069] The completion of the reaction was confirmed through the above nuclear magnetic resonance analysis, and 20g of methylene chloride was added to the obtained crude product, washed with 10g of purified water, and then the methylene chloride was removed through vacuum distillation to obtain the final purified fluorosulfamic acid derivative.
[0070] Yield: 63%, Purity 99.7%
[0071] Example 3
[0072] 116.3 g (2 eq) of fluorosulfonic acid and 100.0 g (1 eq) of tetraethylurea were mixed in a 250 mL round-bottom flask equipped with a condenser and a magnetic stirring bar, and the mixture was heated and stirred at 110 °C for 6 hours under a dry nitrogen atmosphere. The mixture was cooled, and the spectrum of the sample was analyzed by nuclear magnetic resonance analysis.
[0073] The completion of the reaction was confirmed through the aforementioned nuclear magnetic resonance analysis, and the obtained crude product was purified through vacuum distillation.
[0074] Yield: 67%, Purity 99.3%
[0075] Example 4
[0076] 70.5 g (2 eq) of fluorosulfonic acid and 100.0 g (1 eq) of tetrabutylurea were mixed in a 100 mL round-bottom flask equipped with a condenser and a magnetic stirring bar, and the mixture was heated and stirred at 110 °C for 6 hours under a dry nitrogen atmosphere. The mixture was cooled, and the spectrum of the sample was analyzed by nuclear magnetic resonance analysis.
[0077] The completion of the reaction was confirmed through the aforementioned nuclear magnetic resonance analysis, and the obtained crude product was purified through vacuum distillation.
[0078] Yield: 61%, Purity 99.1%
[0079] Example 5
[0080] A fluorosulfamic acid derivative was obtained by performing the same procedure as in Example 1, except that 3 equivalents of fluorosulfonic acid were reacted with 1 equivalent of tetramethylurea.
[0081] The yield and purity are shown in Table 1 below.
[0082] Example 6
[0083] A fluorosulfamic acid derivative was obtained by performing the same procedure as in Example 1, except that 4 equivalents of fluorosulfonic acid were reacted with 1 equivalent of tetramethylurea.
[0084] The yield and purity are shown in Table 1 below.
[0085] Example 7
[0086] A fluorosulfamic acid derivative was obtained by performing the same procedure as in Example 1, except that the reaction temperature was set to 120℃.
[0087] The yield and purity are shown in Table 1 below.
[0088] Example 8
[0089] A fluorosulfamic acid derivative was obtained by performing the same procedure as in Example 1, except that the reaction temperature was set to 140℃.
[0090] The yield and purity are shown in Table 1 below.
[0091] Example Classification Fluorosulfonic acid urea Reaction Temperature Yield Purity Purification 1 Equivalent Ratio 2 eq 1 eq 1 10℃ 70% 99.50% Distillation Purification 2 2 eq 1 eq 63% 99.70% Distillation Purification after washing 3 2 eq 1 eq 67% 99.30% Distillation Purification 4 2 eq 1 eq 61% 99.10% Distillation Purification 5 3 eq 1 eq 83% 99.43% Distillation Purification 6 4 eq 1 eq 82% 99.54% Distillation Purification 7 2 eq 1 eq 1 20℃ 75% 99.70% Distillation Purification 8 2 eq 1 eq 1 40℃ 73% 99.65% Distillation Purification
[0092] According to the method of the present invention, high-purity sulfamic acid derivatives can be produced in high yield using relatively safe reactants under mild conditions.
[0093] The method for producing sulfamic acid derivatives according to the present invention does not use toxic gases such as SO2F2 or SO2FCl, and can produce sulfamic acid derivatives with high purity and high yield due to minimal side reactions. Furthermore, since commercial mass production is possible by not using the expensive reagent known as SuFEx, it has industrial applicability.
Claims
1. A method for preparing a sulfamic acid derivative of the following chemical formula 1, characterized by reacting a urea derivative of the following chemical formula 3 with a fluorosulfonic acid or chlorosulfonic acid. Chemical formula 1 Chemical formula 3 R2R3N-C(=O)-NR2R3 In the above formula, R1 is F or Cl and R2 and R3 are each independently a substituted or unsubstituted linear or branched C1-C24 alkyl group, a substituted or unsubstituted linear or branched C2-C24 alkenyl group, a substituted or unsubstituted C6-C10 aryl group or a substituted or unsubstituted C5-C10 heteroaryl group, and R2 and R3 can combine to form a ring that may or may not contain additional heteroatoms.
2. A method for preparing a sulfamic acid derivative according to claim 1, wherein the reaction between the urea derivative and fluorosulfonic acid or chlorosulfonic acid is carried out under a solvent.
3. A method for preparing a sulfamic acid derivative according to claim 2, wherein the solvent is one or more selected from the group consisting of toluene, benzene, acetonitrile, methylene chloride, and 1,2-dichlorobenzene.
4. A method for preparing a sulfamic acid derivative according to claim 1, wherein the reaction between the urea derivative and fluorosulfonic acid or chlorosulfonic acid is carried out under solvent-free conditions.
5. A method for preparing a sulfamic acid derivative according to claim 1, characterized in that the reaction between the urea derivative and fluorosulfonic acid or chlorosulfonic acid is carried out at 100°C to 160°C.
6. A method for preparing a sulfamic acid derivative according to claim 1, characterized by reacting 2 to 6 equivalents of fluorosulfonic acid or chlorosulfonic acid with 1 equivalent of a urea derivative.
7. A method for manufacturing a sulfamic acid derivative according to claim 1, further comprising a purification step.
8. A method for manufacturing a sulfamic acid derivative according to claim 7, wherein the purification step is a step of dissolving the sulfamic acid derivative in a solvent and then removing the solvent by vacuum distillation.
9. A method for preparing a sulfamic acid derivative according to claim 7, wherein the purification step is a step of dissolving a sulfamic acid derivative in a solvent, washing the obtained solution with purified water or alkaline water, and then removing the solvent by vacuum distillation.
10. A method for preparing a sulfamic acid derivative according to claim 8, wherein the solvent in the purification step is one or more selected from the group consisting of toluene, benzene, acetonitrile, methylene chloride, and 1,2-dichlorobenzene.
11. A method for preparing a sulfamic acid derivative according to claim 9, wherein the solvent in the purification step is one or more selected from the group consisting of toluene, benzene, acetonitrile, methylene chloride, and 1,2-dichlorobenzene.