A preparation method of 1,3-propene sultone

Abstract

The present invention provides a method for preparing 1,3-propylene sultone, comprising the following steps: subjecting 3-hydroxy-1-alkynyl sulfonic acid or its salt to a hydrogenation reduction reaction under the action of a promoter to obtain cis-3-hydroxy-1-alkenyl sulfonic acid or its salt; dehydrating and cyclizing cis-3-hydroxy-1-alkenyl sulfonic acid or its salt to obtain 1,3-propylene sultone, and the reaction structure is as follows:. The present invention provides a novel method for preparing alkynyl sulfonic acid or its salt by a free radical sulfonation reaction using an alkynyl halide as a starting material under illumination. Alkynyl sulfonic acid or its salt is subjected to a selective catalytic hydrogenation reaction to prepare the corresponding cis-alkenyl sulfonic acid or its salt, which is more prone to intramolecular dehydration and cyclization relative to its trans isomer, reduces the temperature of the dehydration reaction, and effectively avoids side reactions such as olefin self-polymerization and product decomposition occurring at high temperatures, so that the yield of the product 1,3-propylene sultone can be greatly improved.

Description

Technical Field

[0001] The present invention relates to the technical field of new energy battery material synthesis, and in particular to a method for preparing 1,3-propylene sultone. Background Art

[0002] 1,3-Propene sultone (PST) is an important fine chemical intermediate. It is widely used in organic synthesis. It can undergo Diels-Alder reaction with diene compounds, and can also undergo 1,3-dipolar cycloaddition reaction with nitrone compounds to generate nitrogen-containing heterocyclic compounds. It can also be used in the preparation of sulfonamide compounds.

[0003] In recent years, 1,3-propene sultone can also be used as a common film-forming additive for lithium-ion battery electrolytes to improve the stability and cycle life of lithium-ion batteries. Adding a small amount of 1,3-propene sultone to the organic electrolyte of lithium-ion batteries can preferentially reduce and decompose on the carbon negative electrode to form a solid electrolyte interface film with excellent performance, effectively inhibiting the continuous decomposition of solvent molecules on the electrode surface, thereby improving the performance of the carbon negative electrode.

[0004] At present, there are several methods for preparing 1,3-propene sultone: (1) Reference (Ger1146870; Synthesis 2003, 9, 1329-1334.) discloses that propargyl alcohol is used as a raw material, and potassium pyrosulfite is used to add and acidify it under free radical conditions to prepare 3-hydroxy-1-propene sulfonic acid, and finally dehydration and cyclization is used to prepare 1,3-propene sultone, but the yield is too low (14.5%); (2) Reference (Tetrahedron 1999, 55, 2245-2262.) reports that allyl chloride / bromine is used as a raw material, first reacts with sodium bisulfite to prepare sodium allyl sulfonate, then reacts with bromine to prepare sodium 2,3-dibromopropane sulfonate, and finally undergoes cyclization and elimination reactions to prepare PST. The actual cyclization yield is also low; (3) Reference (Synthesis 2004, 10, 1696-1712; Tetrahedron 2006, 62, 9017-9037; Chem. Eur. J., 2015, 21, 6906-6912.) reported that vinyl sulfonyl chloride was first reacted with allyl alcohol to prepare allyl vinyl sulfonate, and in the presence of a noble metal catalyst, allyl vinyl sulfonate underwent intramolecular olefin metathesis to prepare 1,3-propylene sultone; (4) Patents WO2011016440 A1 and WO2023075263 A1 disclose a method of using epichlorohydrin as a raw material to first prepare sodium 2,3-dihydroxypropane-1-sulfonate, cyclize to prepare the intermediate 2-hydroxypropane sultone, and finally prepare PST through elimination and dehydration; (5) Reference (Synlett 1998, 1411-1413.) and patent WO2022092834 A1 discloses a method for preparing 2-bromo / chloro-1,3-propane sultone by using allylsulfonyl chloride as a raw material through epoxidation cyclization and halogenation, and then preparing 1,3-propene sultone through elimination reaction under alkaline conditions.

[0005] In summary, there are many literature reports on the synthesis methods of 1,3-propene sultone, but the yields are low. Therefore, a high-yield synthesis method of 1,3-propene sultone is needed, which can be scaled up to a commercial preparation process. Summary of the invention

[0006] In view of the above-mentioned shortcomings of the prior art, the object of the present invention is to provide a method for preparing 1,3-propene sultone, so as to solve the problem of low yield of 1,3-propene sultone in the prior art.

[0007] To achieve the above objectives and other related objectives, the present invention is achieved through the following technical solutions.

[0008] The first aspect of the present invention is to provide a method for preparing an alkynyl sulfonic acid or a salt thereof, the preparation method comprising the following steps: reacting an alkynyl halide represented by formula I, a catalyst and a sulfonylating agent under light and an oxygen-containing atmosphere to obtain an alkynyl sulfonic acid or a salt thereof represented by formula II, the chemical reaction formula being as follows:

[0009] ;

[0010] Wherein, R is selected from any one of H, substituted or unsubstituted straight or branched alkyl, substituted or unsubstituted branched or straight cyclic alkyl, substituted or unsubstituted straight or branched alkenyl, substituted or unsubstituted straight or branched cycloalkenyl, substituted or unsubstituted straight or branched alkynyl, substituted or unsubstituted straight or branched cycloalkynyl, substituted or unsubstituted aryl, nitrogen-containing heteroaryl, substituted or unsubstituted ester; the substituted substituent is selected from any one of hydroxyl, ester, alkyl, cycloalkyl, alkenyl, alkoxy, aryl, aralkyl and heteroaryl;

[0011] X is a halogen atom or other leaving group;

[0012] M is selected from a metal atom or H.

[0013] The second aspect of the present invention is to provide alkynyl sulfonic acid or its salt, which is prepared by the above preparation method.

[0014] The third aspect of the present invention provides a method for preparing an alkene sulfonic acid or a salt thereof, the method comprising the following steps: subjecting the alkene sulfonic acid or a salt thereof prepared by the method for preparing the alkene sulfonic acid or a salt thereof described above to a hydrogenation reduction reaction under the action of a catalyst to obtain an alkene sulfonic acid or a salt thereof represented by formula III, wherein the chemical reaction formula is as follows:

[0015] ;

[0016] Wherein, R is selected from any one of H, substituted or unsubstituted straight or branched alkyl, substituted or unsubstituted branched or straight cyclic alkyl, substituted or unsubstituted straight or branched alkenyl, substituted or unsubstituted straight or branched cycloalkenyl, substituted or unsubstituted straight or branched alkynyl, substituted or unsubstituted straight or branched cycloalkynyl, substituted or unsubstituted aryl, nitrogen-containing heteroaryl, substituted or unsubstituted ester; the substituted substituent is selected from any one of hydroxyl, ester, alkyl, cycloalkyl, alkenyl, alkoxy, aryl, aralkyl and heteroaryl;

[0017] M is selected from a metal atom or H;

[0018] The catalyst is a transition metal catalyst.

[0019] The fourth aspect of the present invention provides an olefin sulfonic acid or a salt thereof, which is prepared by the above-mentioned preparation method.

[0020] A fifth aspect of the present invention provides a method for preparing 1,3-propene sultone, the preparation method comprising the following steps:

[0021] (1) subjecting the alkynyl sulfonic acid or its salt prepared by the above-mentioned preparation method of the alkynyl sulfonic acid or its salt to a hydrogenation reduction reaction under the action of a promoter to obtain cis-3-hydroxy-1-alkenyl sulfonic acid or its salt; the alkynyl sulfonic acid or its salt is a compound represented by formula II-1;

[0022] (2) Dehydrating and cyclizing the cis-3-hydroxy-1-enesulfonic acid or its salt obtained in step (1) to obtain 1,3-propenesulfonate. The reaction structure is as follows:

[0023] ;

[0024] Wherein, M is selected from H or a metal atom.

[0025] As described above, the method for preparing 1,3-propene sultone of the present invention has the following beneficial effects:

[0026] (1) The preparation method of 1,3-propene sultone of the present invention can stably and efficiently produce 1,3-propene sultone which can be used as a non-aqueous electrolyte additive for lithium-ion secondary batteries on an industrial scale;

[0027] (2) The present invention provides a new method for preparing alkynyl sulfonic acid or its salt by a free radical sulfonation reaction under light using alkynyl iodide as a starting material. The alkynyl sulfonic acid or its salt is subjected to a selective catalytic hydrogenation reaction to prepare the corresponding cis-olefin sulfonic acid or its salt, wherein cis-3-hydroxypropylene sulfonic acid or its salt is more susceptible to intramolecular dehydration cyclization than its trans isomer, which greatly reduces the temperature of the dehydration reaction, effectively avoiding side reactions such as olefin self-polymerization and product decomposition at high temperatures, thereby greatly improving the yield of the product 1,3-propylene sulfone. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is shown that the 1,3-propene sultone of the present invention 1 Schematic diagram of H-NMR.

[0029] Figure 2 It is shown that the 1,3-propene sultone of the present invention 13 Schematic diagram of C-NMR. DETAILED DESCRIPTION

[0030] Unless otherwise specified, the following words, phrases and symbols used in this specification generally have the meanings described below.

[0031] In general, the nomenclature used herein (e.g., IUPAC nomenclature) and the laboratory procedures described below (including for cell culture, organic chemistry, analytical chemistry, and pharmacology, etc.) are those well known and commonly used in the art. Unless otherwise defined, all scientific and technical terms used herein in conjunction with the present disclosure described herein have the same meanings as commonly understood by those skilled in the art. In addition, in the claims and / or the specification, when the term "one" or "an" is used in conjunction with the term "comprising" or a noun, its meaning may be "one", but it is also consistent with the meaning of "one or more", "at least one" and "one or more than one". Similarly, the term "another" or "other" can mean at least a second or more.

[0032] It should be understood that whenever various aspects are described herein using the terms “including” or “comprising,” other similar aspects described by “consisting of…” and / or “consisting essentially of…” are also provided.

[0033] In this article, the term "substituted or unsubstituted" used alone or in combination refers to substitution with one or more substituents selected from the following in the present application: deuterium, halogen, cyano, nitro, hydroxyl, sulfhydryl, carbonyl, ester, imido, amino, phosphine oxide group, oxo, alkoxy, trifluoromethoxy, aryloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, silyl, boron, alkyl, cycloalkyl, alkenyl, aryl, aralkyl, aralkenyl, alkylaryl, alkylamino, aralkylamino, heteroarylamino, arylamino, arylphosphino and heteroaryl, acenaphthenyl, or unsubstituted; or substituted with a substituent connecting two or more of the substituents exemplified above, or unsubstituted. For example, "a substituent connecting two or more substituents" may include a biphenyl group, that is, the biphenyl group may be an aryl group, or a substituent connecting two phenyl groups.

[0034] As used herein, the term "alkyl" used alone or in combination may be straight chain or branched, and the number of carbon atoms may be, for example, C1-C10, C1-C9, C1-C8, C1-C7, C1-C5, C1-C4, C1-C3, C1-C2, etc. As examples, alkyl includes, but is not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, etc. In the present disclosure, the "alkyl" is optionally substituted, and the substituted substituent is optionally selected from, for example, deuterium, hydroxyl, amino, thiol, halogen, cyano, nitro, carbonyl, ester, oxo, imido, phosphine oxide, trifluoromethyl, trifluoromethoxy, C1~C3 alkyl, C1-C3 alkoxy and any combination thereof.

[0035] In this article, the term "alkenyl" used alone or in combination includes straight or branched alkenyls, and the number of carbon atoms thereof can be, for example, C2-C10, C3-C10, C2~C5, C2~C4, C2~C3, etc. As an example, alkenyl includes, but is not limited to, vinyl, allyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc. In the present disclosure, the "alkenyl" is an optionally substituted alkenyl. Substituted alkenyl refers to an alkenyl substituted one or more times (e.g., 1-4, 1-3 times, or 1-2 times) by a substituent, and the substituent can be, for example, deuterium, hydroxyl, amino, sulfhydryl, halogen, cyano, nitro, carbonyl, ester, oxo, imido, phosphine oxide, trifluoromethyl, trifluoromethoxy, C1~C3 alkyl, C1-C3 alkoxy, and any combination thereof. Preferred substituents include, for example, -F, -CF3, CH3, -OCH3 and the like.

[0036] In this article, the term "alkynyl" used alone or in combination includes alkynyl groups with straight or branched chains, and the number of carbon atoms thereof can be, for example, C2-C10, C3-C10, C2-C5, C2-C4, C2-C3, etc. As an example, alkynyl groups include ethynyl, propargyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, etc. In the present disclosure, the "alkynyl" is an optionally substituted alkenyl. Substituted alkynyl refers to an alkynyl group substituted one or more times (e.g., 1-4, 1-3 times, or 1-2 times) by a substituent, and the substituent can be, for example, deuterium, hydroxyl, amino, sulfhydryl, halogen, cyano, nitro, carbonyl, ester, oxo, imido, phosphine oxide, trifluoromethyl, trifluoromethoxy, C1-C3 alkyl, C1-C3 alkoxy, and any combination thereof. Preferred substituents include, for example, -F, -CF3, CH3, -OCH3 and the like.

[0037] As used herein, the term "cycloalkyl" used alone or in combination refers to saturated and partially unsaturated (i.e., having one or more double bonds, but not completely conjugated) monocyclic or bicyclic or polycyclic hydrocarbon groups, which in some embodiments have 3 to 10 carbon atoms (i.e., C3-C10 cycloalkyl), 3 to 6 carbon atoms (i.e., C3-C6 cycloalkyl), C3-C5 cycloalkyl, or C3-C4 cycloalkyl, etc. Representative examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, and cyclohexenyl. In the present disclosure, the "cycloalkyl" is optionally substituted, and the substituents are preferably one or more (e.g., 1-5, 1-4, 1-3, 1-2, or 1) selected from deuterium, hydroxyl, amino, thiol, halogen, cyano, nitro, carbonyl, ester, imido, oxo, phosphine oxide, trifluoromethyl, trifluoromethoxy, C1-C3 alkyl, C1-C3 alkoxy and any combination thereof.

[0038] In this article, the term "aryl" used alone or in combination refers to a monovalent carbocyclic aromatic group containing one or more fused rings, such as C5~C10, C6~C10 aryl, etc. The aryl group may be a monocyclic arylene group or a polycyclic arylene group. In some embodiments, monocyclic aryl groups include, but are not limited to, phenyl, biphenyl, etc. Polycyclic aryl groups include, but are not limited to, naphthyl, etc. In the present disclosure, the "aryl group" is an optionally substituted aryl group. Substituted aryl refers to an aryl group substituted one or more times (e.g., 1-4, 1-3 times, or 1-2 times) by a substituent, such as an aryl group monosubstituted, disubstituted, or trisubstituted by a substituent, wherein the substituent group is optionally selected from, for example, deuterium, hydroxyl, amino, thiol, halogen, cyano, nitro, carbonyl, ester group, imido group, oxo group, phosphine oxide group, trifluoromethyl, trifluoromethoxy, C1~C3 alkyl, C1-C3 alkoxy, and any combination thereof.

[0039] As used herein, the term "heteroaryl", alone or in combination, refers to a C5-C10 monocyclic, bicyclic or polycyclic monovalent heteroaryl group containing at least one aromatic ring having 1 or more (e.g., 1 to 4, 1 to 3, or 1 to 2) heteroatoms independently selected from oxygen, nitrogen and sulfur. Heteroaryl includes, but is not limited to, pyridinyl, pyrrolyl, pyrimidinyl, pyridazinyl, furanyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyranyl, thiopyranyl, pyrazinyl, pyridazinyl, thiazinyl, dioxinyl, triazinyl, tetrazinyl, quinolyl, isoquinolyl, quinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, acridinyl, xanthenyl, phenanthridinyl, naphthyridinyl, triazaindenyl, indolyl, indolinyl, indolizinyl, phthalazinyl, pyrazolopyridinyl, pyrazolopyrimidinyl, pyridopy ... The heteroaryl groups may be substituted or unsubstituted. Substituted heteroaryl refers to heteroaryl substituted one or more times (e.g., 1-4, 1-3, or 1-2 times) with substituents, wherein the substituents are optionally selected from deuterium, hydroxyl, amino, thiol, halogen, cyano, nitro, carbonyl, ester, imido, oxo, phosphine oxide, trifluoromethyl, trifluoromethoxy, C1-C3 alkyl, C1-C3 alkoxy, and any combination thereof.

[0040] In this context, the alkynyl halide of the present invention has a structure as shown in (I), , X is a halogen atom or other leaving group.

[0041] In this context, the alkynyl sulfonic acid or its salt of the present invention has a structure as shown in (II), ; M is selected from a metal atom or H.

[0042] Herein, the structure of the 3-hydroxy-1-alkynyl sulfonic acid or its salt of the present invention is ; M is selected from a metal atom or H.

[0043] In this context, the cis-3-hydroxy-1-enesulfonic acid or its salt of the present invention has the structure ; M is selected from a metal atom or H.

[0044] In this context, the alkenyl sulfonic acid or its salt of the present invention has a structure as shown in (III), .

[0045] In this context, the 1,3-propene sultone of the present invention has the structure .

[0046] Sulfonic acid or sulfonate, as the most basic sulfonic acid compound, can be efficiently converted into derivatives such as sulfonyl halides, sulfonamides and sulfones. Therefore, sulfonation is the most common synthetic method for introducing sulfonic acid groups (-SO3M) into molecules. The reaction conditions of traditional sulfonation reactions are relatively harsh, and the commonly used sulfonation reagents are concentrated sulfuric acid, chlorosulfonic acid, fuming sulfuric acid, etc., which have low tolerance to functional groups and poor selectivity. Therefore, the development of a new sulfonation method with mild reaction conditions and high selectivity has important application value.

[0047] For substrates containing unsaturated double bonds or triple bonds in the molecule, the sulfonation reaction needs to be carried out under mild reaction conditions, and the functional groups of the substrates are relatively limited. At present, there are few research reports on the preparation of alkynyl sulfonic acids or alkynyl sulfonates. The literature (Chem. Eur. J., 2010,16, 2528-2536.) reported a method of preparing alkynyl sulfonic acid trimethylsilyl ester and then hydrolyzing it to prepare alkynyl sulfonic acid. Alkynyl sulfonic acid trimethylsilyl ester is prepared by reacting alkynyl trimethylsilyl ether (HC≡CSiMe3) with trimethylsilyl chlorosulfonic acid (ClSO3SiMe3) or sulfur trioxide (SO3·dioxane).

[0048] There is no published literature report on the method of synthesizing alkynyl sulfonic acid / salt by direct CH sulfonation of terminal alkynes and dehalogenation sulfonation of CX bonds.

[0049] The first aspect of the present invention is to provide a method for preparing an alkynyl sulfonic acid or a salt thereof, the preparation method comprising the following steps: reacting an alkynyl halide represented by formula I with a sulfonylating agent under light and an oxygen-containing atmosphere to obtain an alkynyl sulfonic acid or a salt thereof represented by formula II, the chemical reaction formula being as follows:

[0050] ;

[0051] Wherein, R is selected from any one of H, substituted or unsubstituted straight or branched alkyl, substituted or unsubstituted branched or straight cyclic alkyl, substituted or unsubstituted straight or branched alkenyl, substituted or unsubstituted straight or branched cycloalkenyl, substituted or unsubstituted straight or branched alkynyl, substituted or unsubstituted straight or branched cycloalkynyl, substituted or unsubstituted aryl, nitrogen-containing heteroaryl, substituted or unsubstituted ester; the substituted substituent is selected from any one of hydroxyl, ester, alkyl, cycloalkyl, alkenyl, alkoxy, aryl, aralkyl and heteroaryl;

[0052] X is a halogen atom; preferably, the halogen atom is selected from Cl, Br or I; further optionally, the halogen atom is selected from Br or I;

[0053] X is other leaving groups, wherein the leaving group is -OMs or -OTs;

[0054] M is selected from a metal atom or H, wherein the metal atom is selected from Na, K or Li .

[0055] In the preparation method of alkynyl sulfonic acid or its salt provided by the present invention, R is selected from any one of H, substituted or unsubstituted C1-C10 straight or branched alkyl, substituted or unsubstituted C3-C10 branched or straight cyclic alkyl, substituted or unsubstituted C2-C10 straight or branched alkenyl, substituted or unsubstituted C3-C10 straight or branched cycloalkenyl, substituted or unsubstituted C2-C10 straight or branched alkynyl, substituted or unsubstituted C3-C10 straight or branched cycloalkynyl, substituted or unsubstituted C5-C10 aryl, nitrogen-containing heteroaryl, and substituted or unsubstituted ester group; the substituted substituent is selected from any one of hydroxyl, ester group, alkyl, cycloalkyl, alkenyl, alkoxy, aryl, aralkyl and heteroaryl.

[0056] In the preparation method of alkynyl sulfonic acid or its salt provided by the present invention, the R is selected from any one of H, C1-C5 straight or branched alkyl, halogenated C1-C4 alkyl, hydroxy-substituted C1-C10 straight or branched alkyl, C3-C8 branched or straight cyclic alkyl, substituted or unsubstituted C2-C6 straight or branched alkenyl, substituted or unsubstituted C3-C6 straight or branched cycloalkenyl, substituted or unsubstituted C2-C6 straight or branched alkynyl, substituted or unsubstituted C3-C6 straight or branched cycloalkynyl, C5-C10 aryl, methoxy-substituted aryl, halogenated aryl, nitrogen-containing heteroaryl, substituted or unsubstituted ester group; the substituted substituent is selected from any one of hydroxyl, ester group, alkyl, cycloalkyl, alkenyl, alkoxy, aryl, aralkyl and heteroaryl.

[0057] In the method for preparing alkynyl sulfonic acid or its salt provided by the present invention, R is selected from any one of -CH2OH, -CH2CH2OH, -CH2CH2CH3, cycloalkyl, cyclohexyl, phenyl, methoxyphenyl, pyridyl, halogenated aryl, and ester.

[0058] In the method for preparing alkynyl sulfonic acid or its salt provided by the present invention, the reaction process of alkynyl sulfonic acid or its salt is as follows:

[0059] .

[0060] The present invention uses the alkynyl halide shown in formula I as a starting material, and undergoes a free radical sulfinylation reaction with a sulfonylating agent under photoirradiation conditions to obtain an alkynyl sulfinic acid radical, which is instantaneously oxidized to an alkynyl sulfonic acid or a salt thereof shown in formula II in air or an oxygen atmosphere.

[0061] The present invention uses the alkynyl halide shown in formula I as the starting material. The alkynyl halide can generate alkynyl free radicals only under illumination conditions in the absence of a catalyst, and undergoes a free radical coupling reaction with sulfur dioxide free radical anions to prepare an alkynyl sulfone structure. Since the concentration of free radicals generated under photocatalysis is low, the reaction has high selectivity and greatly reduces the occurrence of other side reactions. Compared with traditional electrophilic sulfonation methods, the method can be carried out under mild conditions, has the advantages of good compatibility of substrate functional groups of the reaction, good selectivity, no generation of waste acid, etc., and can convert terminal alkynyl iodide into alkynyl sulfonic acid / salt as shown in formula II with a high yield.

[0062] The alkynyl halide of the present invention can be prepared from the corresponding terminal alkyne (RC≡CH) as a raw material, as shown in reference ( Org. Lett. 2016, 18, 2644-2647; Youji Huaxue 2007, 27, 663-665).

[0063] In the method for preparing alkynyl sulfonic acid or its salt provided by the present invention, the sulfonylating agent is selected from one or more of thiourea dioxide, aminosulfonic acid, sodium pyrosulfite, potassium pyrosulfite, bis(sulfur dioxide)-1,4-diazabicyclo[2,2,2]octane adduct (DABSO), sodium bisulfite, sodium dithionite, sodium hydroxymethylsulfinate, and sodium thiosulfate.

[0064] In the method for preparing alkynyl sulfonic acid or its salt provided by the present invention, the molar ratio of the alkynyl halide represented by formula I to the sulfonylating agent is 1:0.5-2.0. Specifically, it can be 1:0.5-1, 1:1-1.5, 1:1.5-2; typically but not limiting, for example, 1:0.5, 1:1, 1:1.5, 1:2.

[0065] In the method for preparing alkynyl sulfonic acid or its salt provided by the present invention, the catalyst is a phase transfer catalyst, and the phase transfer catalyst is selected from one or more of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetrabutylammonium fluoride, 18-crown-6, and 15-crown-5; the molar ratio of the alkynyl halide represented by formula I to the catalyst is 1:0.001-0.1. Specifically, it can be 1:0.001-0.005, 1:0.005-0.1; typically but not limiting, for example, 1:0.001, 1:0.005, 1:0.1.

[0066] In the preparation method of alkynyl sulfonic acid or its salt provided by the present invention, the reaction is carried out in a solvent, and the solvent is a mixture of an organic solvent and water. Preferably, the organic solvent is selected from one or more of acetonitrile, toluene, tetrahydrofuran, methyltetrahydrofuran, 1,4-dioxane, 1,2-dichloroethane, N-methylpyrrolidone, ethanol, isopropanol, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dimethyl sulfoxide, N, N-dimethylformamide, and N, N-dimethylacetamide; further preferably, the mass ratio of the alkynyl halide represented by formula I to the solvent is 1:2-10. Specifically, it can be 1:2-3, 1:3-6, 1:6-10; typically but not limiting, for example, 1:2, 1:3, 1:6, 1:10.

[0067] In the method for preparing alkynyl sulfonic acid or its salt provided by the present invention, the light source under the illumination condition is selected from ultraviolet light with a wavelength of 300-350nm or visible light with a wavelength of 400-760nm.

[0068] In the method for preparing alkynyl sulfonic acid or its salt provided by the present invention, the oxygen in the oxygen-containing atmosphere comes from air or oxygen.

[0069] In the method for preparing alkynyl sulfonic acid or its salt provided by the present invention, the reaction temperature is 25-35°C; specifically, it can be 25-30°C, 30-35°C; typically but not limitingly, for example, it is 25°C, 30°C, 35°C; the reaction time is 2-24h. Specifically, it can be 2-8h, 8-15h, 15-24h; typically but not limitingly, for example, it is 2h, 8h, 15h, 24h.

[0070] The second aspect of the present invention provides an alkynyl sulfonic acid or a salt thereof, which is prepared by the method of the first aspect of the present invention.

[0071] The present invention provides an alkynyl sulfonic acid or a salt thereof, including but not limited to the following. The structural formula is as follows:

[0072] , wherein M is selected from H or a metal atom.

[0073] The alkynyl sulfonate provided by the present invention includes but is not limited to the following. The structural formula is as follows:

[0074] .

[0075] The third aspect of the present invention provides a method for preparing an alkene sulfonic acid or a salt thereof, the method comprising the following steps: subjecting the alkene sulfonic acid or a salt thereof prepared by the method for preparing the alkene sulfonic acid or a salt thereof described above to a hydrogenation reduction reaction under the action of a catalyst to obtain an alkene sulfonic acid or a salt thereof represented by formula III, the chemical reaction formula being as follows:

[0076] ;

[0077] Wherein, R is selected from any one of H, substituted or unsubstituted straight or branched alkyl, substituted or unsubstituted branched or straight cyclic alkyl, substituted or unsubstituted straight or branched alkenyl, substituted or unsubstituted straight or branched cycloalkenyl, substituted or unsubstituted straight or branched alkynyl, substituted or unsubstituted straight or branched cycloalkynyl, substituted or unsubstituted aryl, nitrogen-containing heteroaryl, substituted or unsubstituted ester; the substituted substituent is selected from any one of hydroxyl, ester, alkyl, cycloalkyl, alkenyl, alkoxy, aryl, aralkyl and heteroaryl;

[0078] M is selected from metal atoms or H; the metal atom is selected from Na, K or Li.

[0079] In the method for preparing alkenyl sulfonic acid or its salt provided by the present invention, the definition of R is the same as that in the above-mentioned method for preparing alkynyl sulfonic acid or its salt.

[0080] In the preparation method of alkenyl sulfonic acid or its salt provided by the present invention, the chemical reaction formula of alkenyl sulfonic acid or its salt is as follows:

[0081] .

[0082] In the preparation method of olefin sulfonic acid or its salt provided by the present invention, the catalyst is a transition metal catalyst, and the transition metal catalyst is one or more of Lindlar catalyst, palladium carbon catalyst, palladium alumina catalyst, preferably, the transition metal catalyst is Lindlar catalyst. Using a selective catalytic hydrogenation catalyst, such as Lindlar catalyst, the reduction ability of the catalyst becomes very mild by "deactivation", and the more active acetylenic bonds can be more stably adsorbed on the surface of the catalyst to undergo hydrogenation reduction reaction, and the reaction stays at the olefin stage to form cis-olefins. In the present invention, by adding a catalytic amount of an organic base such as pyridine in the catalytic reduction system, the catalyst can be further "deactivated", the selectivity of generating olefins is increased, and there is no obvious effect on the sulfonate / sulfonate functional group.

[0083] In the method for preparing olefin sulfonic acid or its salt provided by the present invention, the reaction temperature is 20-60°C; the reaction temperature can be 20-30°C, 30-40°C, 40-50°C, 50-60°C; typically but not limiting, for example, 20°C, 30°C, 40°C, 50°C, 60°C.

[0084] In the method for preparing olefin sulfonic acid or its salt provided by the present invention, the reaction time is 24-48 hours. Specifically, it can be 24-28 hours, 28-35 hours, 35-41 hours, 41-48 hours; typically but not limitingly, for example, it is 24 hours, 28 hours, 35 hours, 41 hours, 48 ​​hours.

[0085] In the method for preparing olefin sulfonic acid or its salt provided by the present invention, the reaction is carried out under normal pressure or under pressure; preferably, the reaction pressure is 1 to 5 atm. Specifically, it can be 1 to 2 atm, 2 to 3 atm, 3 to 5 atm; typically but not limitingly, for example, 1 atm, 2 atm, 3 atm, 5 atm.

[0086] In the method for preparing olefin sulfonic acid or its salt provided by the present invention, the molar ratio of the amount of the catalyst to the alkynyl sulfonic acid or its salt shown in formula II is 0.001-0.1:1; the molar ratio of the amount of the catalyst to the alkynyl sulfonic acid or its salt shown in formula II can be 0.001-0.005:1, 0.005-0.1:1; typically but not limitatively, for example, 0.001:1, 0.005:1, 0.1:1.

[0087] In the method for preparing alkene sulfonic acid or its salt provided by the present invention, the reaction is carried out in the presence of a solvent, the solvent is a mixture of alcohols and water, preferably a mixture of methanol and water; the mass ratio of the alkynyl sulfonic acid or its salt represented by formula II to the solvent is 1:2-5. Specifically, it can be 1:2-3, 1:3-4, 1:4-5; typically but not limiting, for example, 1:2, 1:3, 1:4, 1:5.

[0088] The fourth aspect of the present invention provides an olefin sulfonic acid or a salt thereof, which is prepared by the preparation method of the third aspect of the present invention.

[0089] A fifth aspect of the present invention provides a method for preparing 1,3-propene sultone, the preparation method comprising the following steps:

[0090] (1) subjecting the alkynyl sulfonic acid or its salt prepared by the above-mentioned preparation method of the alkynyl sulfonic acid or its salt to a hydrogenation reduction reaction under the action of a promoter to obtain cis-3-hydroxy-1-alkenyl sulfonic acid or its salt; the alkynyl sulfonic acid or its salt is a compound represented by formula II-1;

[0091] (2) Dehydrating and cyclizing the cis-3-hydroxy-1-enesulfonic acid or its salt obtained in step (1) to obtain 1,3-propenesulfonate. The reaction structure is as follows:

[0092] ;

[0093] Wherein, M is selected from H or a metal atom.

[0094] The alkynyl sulfonic acid or its salt of the present invention undergoes a catalytic hydrogenation reaction under the action of a promoter, and cis-olefin sulfonic acid or its salt can be prepared with high selectivity. After acidification, (Z)-3-hydroxypropylene sulfonic acid or its salt can also be obtained. The (Z)-3-hydroxypropylene sulfonic acid or its salt is dehydrated and cyclized under the action of a dehydrating agent to obtain 1,3-propylene sulfonic acid lactone.

[0095] The present invention provides a new method for preparing alkynyl sulfonic acid or its salt by a free radical sulfonation reaction under light with alkynyl halide as a starting material. The alkynyl sulfonic acid or its salt is subjected to a selective catalytic hydrogenation reaction to prepare the corresponding cis-olefin sulfonic acid or its salt, wherein cis-3-hydroxypropylene sulfonic acid or its salt is more likely to undergo intramolecular dehydration cyclization than its trans isomer, so that the temperature of the dehydration reaction is greatly reduced, and the side reactions such as olefin self-polymerization and product decomposition occurring at high temperature are effectively avoided, so that the yield of the product 1,3-propylene sulfone can be greatly improved.

[0096] In the method for preparing 1,3-propene sultone provided by the present invention, the catalyst in step (1) is a transition metal catalyst, and the transition metal catalyst is one or more of a Lindlar catalyst, a palladium-carbon catalyst, and a palladium-aluminum oxide catalyst. Preferably, the transition metal catalyst is a Lindlar catalyst.

[0097] In the method for preparing 1,3-propene sultone provided by the present invention, the reaction temperature in step (1) is 20-60°C; the reaction temperature can be 20-30°C, 30-40°C, 40-50°C, 50-60°C; typically but not limiting, for example, 20°C, 30°C, 40°C, 50°C, 60°C.

[0098] In the method for preparing 1,3-propene sultone provided by the present invention, the reaction time in step (1) is 24 to 48 hours. Specifically, it can be 24 to 28 hours, 28 to 35 hours, 35 to 41 hours, 41 to 48 hours; typically but not limitingly, for example, it is 24 hours, 28 hours, 35 hours, 41 hours, 48 ​​hours.

[0099] In the method for preparing 1,3-propene sultone provided by the present invention, the reaction in step (1) is carried out under normal pressure or under pressure; preferably, the reaction pressure is 1 to 5 atm. Specifically, it can be 1 to 2 atm, 2 to 3 atm, 3 to 5 atm; typically but not limitingly, for example, 1 atm, 2 atm, 3 atm, 5 atm.

[0100] In the method for preparing 1,3-propene sultone provided by the present invention, the molar ratio of the amount of the promoter to 3-hydroxy-1-alkynyl sulfonic acid or its salt in step (1) is 0.001-0.1:1; the molar ratio of the amount of the catalyst to 3-hydroxy-1-alkynyl sulfonic acid or its salt can be 0.001-0.005:1, 0.005-0.1:1; typically but not limiting, for example, 0.001:1, 0.005:1, 0.1:1.

[0101] In the preparation method of 1,3-propene sultone provided by the present invention, the dehydrating agent used for dehydration cyclization in step (2) is selected from one or more of p-toluenesulfonic acid, concentrated sulfuric acid, fuming sulfuric acid, polyphosphoric acid, SO3, chlorosulfonic acid, P2O5, POCl3, SOCl2 and molecular sieve type dehydrating agent. The molar ratio of the 3-hydroxy-1-alkenylsulfonic acid or its salt to the dehydrating agent is 1:1-10; specifically, it can be 1:1-3, 1:3-6, 1:6-10; typically but not limiting, for example, 1:1, 1:3, 1:6, 1:10.

[0102] When the dehydrating agent is acidic, 3-hydroxy-1-alkynylsulfonic acid or its salt can be directly cyclized to generate 1,3-propenesulfone. Preferably, after step (1), an acidification process is first performed, and then the dehydration cyclization of step (2) is performed.

[0103] In the method for preparing 1,3-propene sultone provided by the present invention, the reaction in step (2) is carried out in the presence of a solvent or in the absence of a solvent. Preferably, the reaction is carried out in the presence of a solvent, and the solvent is a mixture of an organic solvent and water. Preferably, the organic solvent is selected from one or more of benzene, toluene, cyclohexane, methylcyclohexane, dichloromethane, dichloroethane, tetrachloroethane, carbon tetrachloride and chloroform; further preferably, the mass ratio of the 3-hydroxy-1-alkynyl sulfonic acid or its salt to the solvent is 1:2-10. Specifically, it can be 1:2-3, 1:3-4, 1:4-10; typically but not limiting, for example, 1:2, 1:3, 1:4, 1:10.

[0104] The structural formula of 1,3-propene sultone provided by the present invention is as follows:

[0105] .

[0106] The technical solution of the present application is described clearly and completely below in conjunction with the embodiments of the present invention. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by professionals and technicians in this field based on the above-mentioned contents of the present invention still belong to the scope of protection of the present invention.

[0107] In the following examples, the reagents, materials and instruments used are all commercially available unless otherwise specified.

[0108] The yield calculation method in the following examples is actual yield / theoretical yield × 100%, and the purity determination method is gas chromatography, chromatographic column SK-5, chromatographic column temperature 50℃, retention time 2 min, heating rate 10℃ / min to 150℃, and then heating rate 20℃ / min to 300℃, and final temperature retention time 10 min. NMR spectra were obtained on BRUKER400. Unless otherwise specified, the solvents CDCl3, CD3OD and DMSO-d 6 All were purchased from Shanghai Titan Technology Co., Ltd.

[0109] Preparation Example

[0110] This preparation example (refer to Org. Lett. 2016, 18, 2644-2647; Youji Huaxue 2007, 27, 663-665) provides a method for preparing 3-hydroxy-1-propynyl iodide, comprising the following steps:

[0111] Preparation of 3-hydroxy-1-propynyl iodide: Dissolve 50 g of propynyl alcohol (0.89 mol) in 200 mL of acetonitrile and cool to 0 o C, obtain mixed solution 1, dissolve 105 g KOH (1.8 mol) in 100 mL water to obtain mixed solution 2, add mixed solution 2 to mixed solution 1 to obtain mixed solution 3, then add 124 g I2 (0.98 mol) to mixed solution 3, and stir until the reaction is complete. Add an appropriate amount of Na2S2O3 aqueous solution to quench the reaction, concentrate under reduced pressure to evaporate most of the solvent, add ethyl acetate / water (400ml / 200ml) mixture to separate the liquids, separate the organic phase, dry over anhydrous sodium sulfate, filter, and concentrate the filtrate under reduced pressure to obtain a light yellow oily substance, which is 3-hydroxy-1-propynyl iodide, with a mass of 138 g and a yield of 85%. The reaction structure is as follows:

[0112] ;

[0113] The characterization data of 3-hydroxy-1-propynyl iodide are as follows:

[0114] 1 H-NMR (400 MHz, CDCl3): δ 2.04 (t, J = 8.0 Hz, 1H), 4.41 (d, J = 8.0Hz, 2H);

[0115] 13 C-NMR (100 MHz, CD3OD): δ 92.5, 52.6, 2.8. Example 1

[0116] This embodiment provides a method for preparing sodium 3-hydroxy-1-propynyl sulfonate, comprising the following steps:

[0117] 24 g 3-hydroxy-1-propynyl iodide (131 mmol), 26 g sodium dithionite (149 mmol), 240 mg tetrabutylammonium iodide and acetonitrile / H2O (150 ml / 50 mL) mixture were added to a 500 mL dry quartz reaction tube in sequence. The reaction was carried out at room temperature for 24 h under the irradiation of a 50W LED lamp (400-760 nm) and air atmosphere. The reaction raw materials were completely converted by TLC detection. The solvent was removed by vacuum concentration to obtain a crude product. The crude product was crystallized and purified by a mixture of ethanol / H2O to obtain an off-white solid, namely sodium 3-hydroxy-1-propynyl sulfonate, with a mass of 18 g and a yield of 87%. The reaction structure is as follows:

[0118] .

[0119] The characterization data of sodium 3-hydroxy-1-propynyl sulfonate are as follows:

[0120] 1 H-NMR (400 MHz, D2O): δ 4.27 (s, 2H);

[0121] 13 C-NMR (101 MHz, D2O): δ 86.3, 78.0, 49.4. Example 2

[0122] This embodiment provides a method for preparing hexynyl-1-sulfonic acid, comprising the following steps:

[0123] 12g 1-iodo-1-hexyne (57.7 mmol), 8.5g bis(sulfur dioxide)-1,4-diazabicyclo[2,2,2]octane adduct (35.4 mmol), 21 mg tetrabutylammonium iodide and acetonitrile / water (50ml / 30ml) were mixed to obtain a mixed solution, which was placed in a quartz glass tube reactor and stirred under light of 300-350 nm at room temperature. TLC detected that the reaction raw materials were completely converted. The reaction solution was concentrated under reduced pressure to obtain a crude product. 10ml methanol was added to the crude product area for pulping, filtration, and vacuum drying to obtain a white solid, namely hexynyl-1-sulfonic acid, with a mass of 6.8 g and a yield of 64%. The reaction structure is as follows:

[0124] .

[0125] The characterization data of hexynyl-1-sulfonic acid are as follows:

[0126] 1 H-NMR (400 MHz, D2O): δ 2.32 (t, J = 7.0 Hz, 2H), 1.50-1.55 (m, 2H), 1.34-1.28 (m, 2H), 0.86 (t, J = 7.4 Hz, 3H);

[0127] 13 C-NMR (101 MHz, D2O): δ 96.6, 78.0, 28.7, 21.6, 18.4, 13.3. Example 3

[0128] This embodiment provides a method for preparing 2-cyclohexylethynyl sulfonic acid, comprising the following steps:

[0129] Add 18 g of 2-cyclohexylethynyl iodide (76.9 mmol), 10 g of thiourea dioxide (92.5 mmol), 28 mg of tetrabutylammonium iodide and a mixture of acetonitrile / H2O (80 ml / 40 mL) to a quartz reaction tube, and react at room temperature under the irradiation of a 50W LED lamp (400-760 nm) in an air atmosphere. TLC detection shows that the reaction raw materials are completely converted, and the solvent is removed by vacuum concentration. The crude product is crystallized and purified by a mixture solvent of ethanol / H2O (30 mL / 15 mL) to obtain a white solid, namely 3-hydroxy-1-propynyl sulfonic acid, with a mass of 13 g and a yield of 80%. The reaction structure is as follows:

[0130] .

[0131] The characterization data of 2-cyclohexylethynylsulfonic acid are as follows:

[0132] 1 H-NMR (400 MHz, D2O): δ 2.54-2.50 (m, 1H), 1.78-1.72 (m, 2H), 1.64-1.60 (m, 2H), 1.52-1.40 (m, 3H), 1.36-1.08 (m, 3H). Example 4

[0133] This embodiment provides a method for preparing 3-methoxy-1-propynyl sulfonic acid, comprising the following steps:

[0134] 8.0 g 1-iodo-3-methoxypropyne (40.8 mmol), 6.0 g bis(sulfur dioxide)-1,4-diazabicyclo[2,2,2]octane adduct (25 mmol), 15 mg tetrabutylammonium iodide and acetonitrile / H2O (20 ml / 10 mL) were mixed to obtain a mixed solution, which was placed in a quartz glass tube reactor and stirred under light of 300-350 nm at room temperature. TLC detected that the reaction raw materials were completely converted. The reaction solution was concentrated under reduced pressure to obtain a crude product, which was added to a mixture of 8 ml methanol and 40 ml water for pulping, filtered, and vacuum dried to obtain a white solid, namely 3-methoxy-1-propynyl sulfonic acid, with a mass of 6.8 g and a yield of 64%. The reaction structure is as follows:

[0135] .

[0136] The characterization data of 3-methoxy-1-propynyl sulfonic acid are as follows:

[0137] 1 H-NMR (400 MHz, D2O): δ 4.24 (s, 2H), 3.38 (s, 3H);

[0138] 13 C-NMR (101 MHz, D2O): δ 86.3, 83.4, 62.0, 60.8. Example 5

[0139] This embodiment provides a method for preparing sodium 2-phenylethynyl-1-sulfonate, comprising the following steps:

[0140] 12.0 g of phenylethynyl iodide (52.6 mmol), 11.0 g of sodium dithionite (63.2 mmol), 70 mg of 18-crown-6 and acetonitrile / H2O (50 ml / 40 mL) were mixed to obtain a mixed solution, which was placed in a quartz glass tube reactor and stirred under light of 300-350 nm at room temperature in an air atmosphere. TLC detected that the reaction raw materials were completely converted. The reaction solution was concentrated under reduced pressure to obtain a crude product, and the crude product was added to a mixture of 10 mL of methanol and 5 mL of water for slurrying, filtered, and vacuum dried to obtain a white solid, namely 2-phenylethynyl-1-sodium sulfonate, with a mass of 9.0 g and a yield of 84%. The reaction structure is as follows:

[0141] .

[0142] The characterization data of sodium 2-phenylethynyl-1-sulfonate are as follows:

[0143] 1 H-NMR (400 MHz, D2O): δ 7.63-7.59 (m, 2H), 7.56-7.51 (m, 1H), 7.45 7.41(m, 2H);

[0144] 13 C-NMR (101 MHz, D2O): δ 152.3, 131.5, 121.3, 116.1, 86.7, 84.2. Example 6

[0145] This embodiment provides a method for preparing 2-(4-methoxyphenyl)ethynyl-1-sulfonic acid, comprising the following steps:

[0146] 14.0 g of 4-methoxyphenylethynyl iodide (54.2 mmol, 1.0 equiv), 7.0 g of thiourea dioxide (64.7 mmol, 1.2 equiv), 20 mg of tetrabutylammonium iodide (TBAI) and a mixture of acetonitrile / water (50 mL / 40 ml) were mixed to obtain a mixed solution, which was placed in a quartz glass tube reactor and stirred under light of 300-350 nm at room temperature in an air atmosphere. The reaction raw materials were completely converted by TLC detection. The reaction solution was concentrated under reduced pressure to obtain a crude product, which was added to a mixture of 10 mL of methanol and 5 mL of water for slurrying, filtered, and vacuum dried to obtain a white solid, namely 2-phenylethynyl-1-sulfonic acid, with a mass of 10 g and a yield of 80%. The reaction structure is as follows:

[0147] .

[0148] The characterization data of 2-(4-methoxyphenyl)ethynyl-1-sulfonic acid are as follows:

[0149] 1 H-NMR (400 MHz, D2O): δ 7.92 (d, J = 8.8 Hz, 2H), 7.01 (d, J = 8.8 Hz, 2H), 3.86 (s, 3H);

[0150] 13 C-NMR (101 MHz, D2O): δ 162.6, 136.4, 130.4, 117.0, 56.8. Example 7

[0151] This embodiment provides a method for preparing sodium 2-(4-fluorophenyl)ethynyl-1-sulfonate, comprising the following steps:

[0152] 8.0 g of p-fluorophenylacetylene iodine (32.5 mmol, 1.0 equiv), 5.2 g of sodium hydroxymethyl sulfonate (38.8 mmol, 1.2 equiv), 60 mg of tetrabutylammonium iodide (TBAI) and a mixture of acetonitrile / water (50 mL / 20 mL) were added to a 100 mL dry quartz glass reaction tube, and the reaction was stirred at room temperature under the irradiation of a 50 W LED lamp (400-760 nm). TLC detected that the reaction raw materials were completely converted, filtered, and the filtrate was concentrated under reduced pressure to remove the solvent to obtain a crude product. The crude product was crystallized and purified using 80 mL of 50% ethanol aqueous solution to obtain 2-(4-fluorophenyl)ethynyl-1-sulfonate sodium, with a mass of 5.6 g and a yield of 77%. The reaction structure is as follows:

[0153] .

[0154] The characterization data of sodium 2-(4-fluorophenyl)ethynyl-1-sulfonate are as follows:

[0155] 1 H-NMR (400 MHz, D2O): δ 7.74-7.60 (m, 2H), 7.20-7.14 (m, 2H);

[0156] 19 F NMR (376 MHz, DO) δ -101.9. Example 8

[0157] This embodiment provides a method for preparing sodium (Z)-3-hydroxy-1-propene sulfonate, comprising the following steps:

[0158] 200 g of sodium 3-hydroxy-1-propynyl sulfonate was dissolved in 1000 mL of 80% methanol aqueous solution to obtain a mixed solution. 20 g of Ni catalyst (Nickel, Cat. A-70) was added to the mixed solution under nitrogen protection to obtain a mixture. The mixture was then replaced with hydrogen three times. The hydrogen pressure of the reaction equipment was increased to 5 atm. The reaction was stirred at room temperature. The raw material conversion was controlled to be complete by TLC, which took 30 hours. After the reaction was completed, the nitrogen was replaced once, the catalyst was filtered and recovered, the filtrate was concentrated under reduced pressure, filtered, the filter cake was washed once with 200 mL of methanol, and vacuum dried to obtain a white solid, namely (Z)-3-hydroxy-1-propynyl sodium sulfonate, with a mass of 190 g and a yield of 94%. Among them, the methanol aqueous solution is composed of methanol and water in a mass ratio of 8:2. The reaction structure is as follows:

[0159] .

[0160] The characterization data of sodium (Z)-3-hydroxy-1-propylene sulfonate are as follows:

[0161] 1 H-NMR (400 MHz, D2O): δ 6.27 (dt, J1= 12.0 Hz, J2= 4.0 Hz, 1H), 6.09-6.03 (m, 1H), 4.48 (dd, J1= 4.0 Hz, J2= 4.0 Hz, 2H);

[0162] 13 C-NMR (100 MHz, D2O): δ 138.9, 130.0, 57.6. Example 9

[0163] This embodiment provides a method for preparing sodium (Z)-3-hydroxy-1-propene sulfonate, comprising the following steps:

[0164] Dissolve 200g of sodium 3-hydroxy-1-propynyl sulfonate in 400ml of 50% methanol aqueous solution, add 20g of Lindler catalyst (Pd / CaCO3, H84798) under nitrogen protection to obtain a mixture, then replace the mixture with hydrogen three times, add hydrogen pressure to the reaction equipment to 2atm, stir and react at room temperature, and control the conversion of the raw materials in TLC for 24h. After the reaction is complete, replace with nitrogen once, filter and recover the catalyst, concentrate the filtrate under reduced pressure, filter, wash the filter cake with 200mL of methanol, and vacuum dry to obtain a white solid, namely (Z)-3-hydroxy-1-propynyl sodium sulfonate, with a mass of 194 g and a yield of 96%. The reaction structure is as follows:

[0165] . Example 10

[0166] This embodiment provides a method for preparing 1,3-propene sultone, comprising the following steps:

[0167] Mix 120 g of sodium (Z)-3-hydroxy-1-propenesulfonate with 250 mL of POCl3 to obtain a mixture, and heat to 100°C with stirring. o C for about 8h, TLC controlled the complete conversion of the raw materials, evaporated POCl3 under reduced pressure, added dichloroethane and water to the residue to dissolve, allowed to stand for separation, separated the organic phase, dried over anhydrous magnesium sulfate, decolorized with activated carbon, and filtered. The filtrate was concentrated under reduced pressure, and then heptane was added to the concentrated residue to precipitate a large amount of white solids, which were filtered and vacuum dried to obtain 1, 3-propene sultone, with a mass of 64 g, a yield of 71%, and a purity of 99.5%. The reaction structure is as follows:

[0168] .

[0169] Characterization data of 1,3-propene sultone Figure 1 and Figure 2 As shown:

[0170] 1 H NMR (400 MHz, CDCl3): δ7.02-7.00 (dt, J = 6.8 Hz, 2.0 Hz, 1H), 6.81-6.78 (dt, J = 6.8 Hz, 2.4 Hz, 1H), 5.10 (dd, J = 2.0 Hz, 0.8 Hz, 2H);

[0171] 13 C NMR (101 MHz, CDCl3): δ 136.8, 124.4, 72.3. Embodiment 11

[0172] This embodiment provides a method for preparing 1,3-propene sultone, comprising the following steps:

[0173] 130 g of sodium (Z)-3-hydroxy-1-propenesulfonate was mixed with 500 mL of anhydrous dichloroethane to obtain a mixture, the mixture was placed in a 1 L reaction bottle, 70 mL of SOCl2 was added dropwise thereto to obtain a mixed solution, and the mixed solution was heated to 75 oC for 10 h, and the conversion of the raw material was completely controlled by TLC. The reaction solution was cooled to room temperature, and 100 mL of ice water was slowly added dropwise to quench the reaction. The mixture was allowed to stand for 0.5 h, and the organic phase was separated. The organic phase was dried over anhydrous magnesium sulfate, decolorized with activated carbon, and filtered. The filtrate was concentrated under reduced pressure to a total volume of 150 mL, and cooled to 0-5 o C for crystallization for 0.5 h, filter the solid, and vacuum dry to obtain 1,3-propene sultone with a mass of 78 g, a yield of 80%, and a purity of 99.3%. The reaction structure is as follows:

[0174] . Example 12

[0175] This embodiment provides a method for preparing 1,3-propene sultone, comprising the following steps:

[0176] 180 g of sodium (Z)-3-hydroxy-1-propenesulfonate was placed in a 2 L reaction bottle, 900 mL of anhydrous dichloroethane was added, and 20 mL of 20% fuming sulfuric acid was added dropwise under stirring to obtain a mixture, and the mixture was heated to 80 o The reaction was carried out at 40 °C for 2 h. The raw material was completely converted as shown in TLC. The residue was quenched with dichloroethane and ice water, and the mixture was allowed to stand for separation. The lower organic phase was separated, and the organic phase was washed twice with deionized water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to recover most of the solvent. Then heptane was added and the mixture was cooled to 0-5 °C. o C for 0.5h, a large amount of white solid precipitated, filtered, and vacuum dried to obtain 1, 3-propene sultone with a mass of 116 g, a yield of 86%, and a purity of 99.8%. The reaction structure is as follows:

[0177] . Example 13

[0178] This embodiment provides a method for preparing 1,3-propene sultone, comprising the following steps:

[0179] 120 g of (Z)-3-hydroxy-1-propenesulfonic acid was mixed with 480 mL of anhydrous dichloroethane to obtain a mixture, the mixture was placed in a 1 L reaction bottle, 155 g of SOCl2 was added dropwise thereto to obtain a mixed solution, and the mixed solution was heated to 40 o C for 4 h, and the conversion of the raw material was completely controlled by TLC. The reaction solution was cooled to room temperature, and 100 mL of ice water was slowly added dropwise to quench the reaction. The mixture was allowed to stand for 0.5 h, and the organic phase was separated. The organic phase was dried over anhydrous magnesium sulfate, decolorized with activated carbon, and filtered. The filtrate was concentrated under reduced pressure to a total volume of 140 mL, and cooled to 0-5 oC for crystallization for 0.5 h, filter the solid, and vacuum dry to obtain 1,3-propene sultone with a mass of 88.7 g, a yield of 85%, and a purity of 99.5%. The reaction structure is as follows:

[0180] .

[0181] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A method for preparing an alkynyl sulfonic acid or a salt thereof, characterized in that: The preparation method comprises the following steps: reacting an alkynyl halide shown in formula I, a catalyst and a sulfonylating agent under light and an oxygen-containing atmosphere to obtain an alkynyl sulfonic acid or a salt thereof shown in formula II, and the chemical reaction formula is as follows: ； Wherein, R is selected from any one of H, C1-C5 straight or branched alkyl, halogenated C1-C4 alkyl, hydroxy-substituted C1-C10 straight or branched alkyl, C3-C8 branched or straight cyclic alkyl, C5-C10 aryl, methoxy-substituted C5-C10 aryl, and halogenated C5-C10 aryl; X is a halogen atom; M is selected from a metal atom or H; The sulfonylating agent is selected from one or more of thiourea dioxide, bis(sulfur dioxide)-1,4-diazabicyclo[2,2,2]octane adduct, and sodium dithionite; The catalyst is a phase transfer catalyst, and the phase transfer catalyst is selected from one or more of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetrabutylammonium fluoride, and 18-crown-6; The reaction is carried out in a solvent, and the solvent is a mixture of an organic solvent and water; The light source under the illumination condition is selected from ultraviolet light with a wavelength of 300-350nm or visible light with a wavelength of 400-760nm.

2. The method for preparing an alkynyl sulfonic acid or a salt thereof according to claim 1, characterized in that: Also includes any one or more of the following features: A1) the halogen atom is selected from Cl, Br or I; A2) The metal atom is selected from Na, K or Li; A3) the molar ratio of the alkynyl halide represented by formula I to the sulfonylating agent is 1:0.5-2.0; A4) the molar ratio of the alkynyl halide represented by formula I to the catalyst is 1:0.001-0.1; A5) the organic solvent is selected from one or more of acetonitrile, toluene, tetrahydrofuran, methyltetrahydrofuran, 1,4-dioxane, 1,2-dichloroethane, N-methylpyrrolidone, ethanol, isopropanol, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide; A6) The oxygen in the oxygen-containing atmosphere comes from air or oxygen; A7) The reaction temperature is 25-35°C; the reaction time is 2-24h.

3. A method for preparing an olefin sulfonic acid or a salt thereof, characterized in that: The preparation method comprises the following steps: (1) preparing an alkynyl sulfonic acid or a salt thereof by the method for preparing an alkynyl sulfonic acid or a salt thereof according to any one of claims 1 to 2; (2) The alkynyl sulfonic acid or its salt obtained in step (1) is subjected to a hydrogenation reduction reaction in the presence of a catalyst to obtain an alkene sulfonic acid or its salt represented by formula III. The chemical reaction formula is as follows: ； Wherein, R is selected from any one of H, C1-C5 straight or branched alkyl, halogenated C1-C4 alkyl, hydroxy-substituted C1-C10 straight or branched alkyl, C3-C8 branched or straight cyclic alkyl, C5-C10 aryl, methoxy-substituted C5-C10 aryl, and halogenated C5-C10 aryl; M is selected from a metal atom or H; The catalyst in step (2) is a transition metal catalyst.

4. The method for preparing an olefin sulfonic acid or a salt thereof according to claim 3, characterized in that: The step (2) further includes any one or more of the following features: B1) The metal atom is selected from Na, K or Li; B2) the transition metal catalyst is one or more of a Lindlar catalyst, a palladium-carbon catalyst, and a palladium-aluminum oxide catalyst; B3) the reaction temperature is 20-60°C; the reaction time is 24-48h; B4) the reaction is carried out under pressure, the pressure of the reaction is 1 to 5 atm; B5) the molar ratio of the amount of the catalyst to the alkynyl sulfonic acid or its salt represented by formula II is 0.001 to 0.1:1; B6) the reaction is carried out in a solvent, and the mass ratio of the alkynyl sulfonic acid or its salt represented by formula II to the solvent is 1:2-5; B7) The reaction is carried out in a solvent, which is a mixture of alcohol and water.

5. A method for preparing 1,3-propene sultone, characterized in that: The preparation method comprises the following steps: (1) preparing an alkynyl sulfonic acid or a salt thereof by the method for preparing an alkynyl sulfonic acid or a salt thereof according to any one of claims 1 to 2; (2) subjecting the alkynyl sulfonic acid or its salt obtained in step (1) to a hydrogenation reduction reaction under the action of a promoter to obtain cis-3-hydroxy-1-alkenyl sulfonic acid or its salt; the alkynyl sulfonic acid or its salt is a compound represented by formula II-1; (3) Dehydrating and cyclizing the cis-3-hydroxy-1-enesulfonic acid or its salt obtained in step (2) to obtain 1,3-propenesulfonate. The reaction formulas of step (2) and step (3) are as follows: ； Wherein, M is selected from a metal atom or H.

6. The method for preparing 1,3-propene sultone according to claim 5, characterized in that: Also includes any one or more of the following features: C1) The promoter in step (2) is a transition metal catalyst, and the transition metal catalyst is one or more of a Lindlar catalyst, a palladium-carbon catalyst, and a palladium-aluminum oxide catalyst; C2) The reaction temperature in step (2) is 20-60°C; the reaction time is 24-48h; C3) The reaction in step (2) is carried out under pressure, and the reaction pressure is 1 to 5 atm; C4) performing an acidification reaction in step (2); C5) the molar ratio of the amount of the promoter used in step (2) to 3-hydroxy-1-alkynylsulfonic acid or its salt is 0.001 to 0.1:1; C6) the reaction in step (2) is carried out in a solvent, and the mass ratio of 3-hydroxy-1-alkynyl sulfonic acid or its salt to the solvent in step (2) is 1:2-5; C7) the reaction in step (2) is carried out in a solvent, wherein the solvent is a mixture of alcohol and water; C8) The dehydrating agent used for dehydration cyclization in step (3) is selected from one or more of p-toluenesulfonic acid, concentrated sulfuric acid, fuming sulfuric acid, polyphosphoric acid, SO3, chlorosulfonic acid, P2O5, POCl3, SOCl2 and molecular sieve type dehydrating agent; the molar ratio of 3-hydroxy-1-alkenylsulfonic acid or its salt to the dehydrating agent in step (3) is 1:1-10; C9) The reaction temperature of the dehydration cyclization in step (3) is 60-150°C, and the reaction time is 2-10h; C10) the reaction in step (3) is carried out in a solvent, wherein the solvent is one or more selected from the group consisting of benzene, toluene, cyclohexane, methylcyclohexane, dichloromethane, dichloroethane, tetrachloroethane, carbon tetrachloride and chloroform; C11) The reaction in step (3) is carried out in a solvent, and the mass ratio of the 3-hydroxy-1-enesulfonic acid or its salt to the solvent is 1:2-10.

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