CN115925589A - Aliphatic sulfinic acid calcium salt and preparation method thereof - Google Patents
Aliphatic sulfinic acid calcium salt and preparation method thereof Download PDFInfo
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- CN115925589A CN115925589A CN202211672719.0A CN202211672719A CN115925589A CN 115925589 A CN115925589 A CN 115925589A CN 202211672719 A CN202211672719 A CN 202211672719A CN 115925589 A CN115925589 A CN 115925589A
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- -1 Aliphatic sulfinic acid calcium salt Chemical class 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 150000007524 organic acids Chemical class 0.000 claims abstract description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims abstract description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 4
- 238000004537 pulping Methods 0.000 claims abstract description 4
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000003158 alcohol group Chemical group 0.000 claims abstract description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 3
- 239000001110 calcium chloride Substances 0.000 claims abstract description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000292 calcium oxide Substances 0.000 claims abstract description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000001033 ether group Chemical group 0.000 claims abstract description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims abstract description 3
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims abstract description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims abstract description 3
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 description 43
- 150000001875 compounds Chemical class 0.000 description 19
- 239000000243 solution Substances 0.000 description 16
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 10
- FWOHDAGPWDEWIB-UHFFFAOYSA-N 2-bromoethoxymethylbenzene Chemical compound BrCCOCC1=CC=CC=C1 FWOHDAGPWDEWIB-UHFFFAOYSA-N 0.000 description 10
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000003455 sulfinic acids Chemical class 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000011913 photoredox catalysis Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical class ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an aliphatic sulfinic acid calcium salt and a preparation method thereof, and the preparation method comprises the following preparation steps: step 1) in the first step, aliphatic sulfinic acid sodium salt (V) is in acidity to obtain a formula VI; the acid is any one or more of inorganic acid and organic acid; wherein the inorganic acid is preferably hydrochloric acid, sulfuric acid, potassium bisulfate, sodium bisulfate; the organic acid is preferably trifluoroacetic acid, methanesulfonic acid and p-toluenesulfonic acid; the solvent is an ether or ester or a solvent with the water content of toluene being less than 5%; step 2) directly adding calcium ions to obtain an aliphatic sulfinic acid calcium salt (VII); the calcium ions are derived from any one or more of calcium hydroxide, calcium oxide, calcium carbonate and calcium chloride; the pulping solvent is alcohol or a mixture of alcohol and water; the preparation method of the aliphatic sulfinic acid calcium salt has the characteristics of higher quality, higher yield, simple and convenient operation and suitability for industrial production.
Description
Technical Field
The invention relates to the technical field of medicine synthesis, and relates to an aliphatic sulfinic acid calcium salt and a preparation method thereof.
Background
The sodium sulfinate salt is the basic form of sulfinic acid and constitutes a key intermediate in organic synthesis due to its stability. The preparation of sodium alkyl sulfinates remains a challenge in view of the limited commercial availability of aliphatic derivatives and several disadvantages of their synthesis.
Sulfinic acid is a highly reactive and unstable compound, usually generated in situ from its corresponding sodium salt, i.e. sodium sulfinate. These latter molecules have been studied extensively over the last decades, in particular their stability. Furthermore, the dual reactivity of sulfinic acids as salts of electrophilic or nucleophilic substances makes them useful as universal intermediates in organic chemistry.
Sulfinic acids can be involved in the synthesis of sulfones, key components of pharmaceutical chemistry, and can be obtained by thio-alkylation, substitution, photoredox catalysis, metal-catalyzed allyl or benzyl substitution, hydrosulphonation of alkynes, oxysulphonation of alkenes, metal-catalyzed or metal-free coupling, hydrocarbon functionalization or metal-free sulphonation. Sulfinates also constitute sulfonamide precursors by their conversion to sulfonyl chlorides or sulfonyl hydrazides.
The literature is reviewed as follows:
in 2018, tran and the like take benzyl-2-bromoethyl ether (I) and 2-mercaptobenzothiazole (II) as raw materials, and prepare sodium sulfinate (V) through 3 steps of reactions such as alkylation, oxidation and reduction, the yield of the route is 45 percent, and the raw materials such as sodium hydrogen, m-chloroperoxybenzoic acid and the like are used, so the method is extremely easy to ignite and explode, is dangerous and is not suitable for industrial production.
The existing synthetic route has the defects of low yield, and the problems of flammable and explosive hazardous reagents or production process, serious environmental pollution and the like, which are not beneficial to large-scale industrial production.
In conclusion, the method has the advantages of simple reaction, low cost, environmental protection and urgent need for the method for preparing the aliphatic sulfinic acid sodium salt, which is easy for industrial production.
Disclosure of Invention
The technical problem to be solved by the invention is as follows:
the synthesis method of the 2-alkyl sulfonyl benzothiazole, which has the advantages of simple reaction, low cost, environmental protection, good quality and simple and convenient operation and is suitable for industrial production, is developed; finally, the aliphatic sulfinic acid sodium salt can also reach the aliphatic sulfinic acid sodium salt with higher quality, higher yield and simple and convenient operation, and is suitable for industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
the specific synthetic process is as follows:
an aliphatic sulfinic acid calcium salt is provided,
the structural formula of the aliphatic sulfinic acid calcium salt is as follows:
wherein X is methylene or oxygen atom, R is hydrogen, alkyl, benzyl;
as a further preferred embodiment, X is an oxygen atom and R is benzyl.
The preparation method of the aliphatic sulfinic acid calcium salt comprises the following preparation steps:
step 1)
In the first step, the aliphatic sulfinic acid sodium salt (V) is in acid condition to obtain formula VI;
the acid is any one or more of inorganic acid and organic acid; wherein the inorganic acid is preferably hydrochloric acid, sulfuric acid, potassium bisulfate, sodium bisulfate; the organic acid is preferably trifluoroacetic acid, methanesulfonic acid and p-toluenesulfonic acid;
the solvent is an ether or ester or toluene solvent with the water content of less than 5 percent;
step 2)
Directly adding calcium ions to obtain an aliphatic sulfinic acid calcium salt (VII);
the calcium ions are derived from any one or more of calcium hydroxide, calcium oxide, calcium carbonate and calcium chloride;
the pulping solvent is alcohol or a mixture of alcohol and water;
as a further preferred embodiment, the inorganic acid in step 1) is hydrochloric acid, and the molar ratio of the sulfinic acid sodium salt compound (V) to the hydrochloric acid reagent is 1.
As a further preferred embodiment, the inorganic acid in step 1) is hydrochloric acid, the ethers are methyl tert-butyl ether and 2-methyl tetrahydrofuran, and the esters are any one or more of ethyl acetate, isopropyl acetate, n-butyl acetate and isobutyl acetate.
As a further preferred embodiment, the calcium ion source in step 2) is preferably calcium hydroxide, and the molar ratio of the sulfinic acid sodium salt compound (V) to the calcium hydroxide reagent is 1.
As a further preferred embodiment, the alcohol in step 2) is any one or more of methanol, ethanol and isopropanol.
As a further preferred embodiment, the mass ratio of ethanol to water in step 2) is from 80 to 95
As a further preferred embodiment, the mass ratio of ethanol to water in step 2) is 80 to 95, and the purity of the sulfinic acid calcium salt compound (VII) can be as high as 99.5% or more.
A method for preparing aliphatic sulfinic acid sodium salt,
comprises the following synthetic steps:
step 1)
Carrying out alkylation reaction on benzyl-2-bromoethyl ether (I) and 2-mercaptobenzothiazole (II) under alkalinity to obtain a formula III;
step 2)
Directly adding into an oxidation reactor 21137for sulfur oxidation reaction to obtain a formula IV;
step 3)
Thirdly, removing benzothiazole through sodium borohydride to obtain the aliphatic sulfinic acid sodium salt (V);
wherein the reaction formulas of the steps 1) to 3) are as follows:
the method for synthesizing the aliphatic sulfinic acid calcium salt has the following advantages:
1) The invention can obtain the aliphatic sulfinic acid calcium salt, the purity of the aliphatic sulfinic acid calcium salt is superior to that of the aliphatic sulfinic acid sodium salt, and the invention is beneficial to the subsequent application;
2) The invention uses hydrochloric acid to acidify, extract and layer to obtain sulfinic acid solution, the sulfinic acid solution directly generates precipitate with calcium hydroxide, calcium sulfinate (VII) is obtained by filtering, and the calcium sulfinate can be pulped and purified in alcohol and water by utilizing solubility.
3) The method has the advantages of relatively simple route, simple reaction, low cost, environmental protection, better quality and simple and convenient operation, so that the aliphatic sulfinic acid calcium salt also can achieve higher quality, higher yield and simple and convenient operation, and is suitable for industrial production of the aliphatic sulfinic acid calcium salt; provides a new synthesis scheme for the synthesis and preparation of the aliphatic sulfinic acid calcium salt;
drawings
FIG. 1 NMR spectra of comparative example 1 of the invention;
FIG. 2 NMR spectra of comparative example 2 of the present invention;
FIG. 3 NMR spectra of example 3 of the invention;
FIG. 4 NMR spectra of inventive example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clear, the present invention is further described with reference to the following embodiments:
the synthetic route of the aliphatic sulfinic acid calcium salt is as follows
Comparative example 1
A reaction flask was charged with 10g of 2-mercaptobenzothiazole (I) (0.060mol, 1.0eq) and 100mL of dimethylformamide, and 4.3g of sodium hydride (0.072mol, 1.2eq) was added to the reaction solution in portions under ice bath, and the reaction was allowed to proceed for at least 15 minutes under incubation. 14.1g of benzyl-2-bromoethyl ether (II) (0.066 mol, 1.1eq) was added dropwise to the reaction solution, and the reaction was allowed to proceed for at least 2 hours while maintaining the temperature. After the reaction, methyl t-butyl ether was added to the reaction solution to extract twice, the combined organic layers were extracted with water and a 15% aqueous solution of sodium chloride, respectively, and rotary evaporation was carried out under reduced pressure to obtain 18.5g of compound (III). The nuclear magnetic data are as follows: 1 H NMR(CDCl 3 400 MHz) δ 7.85 (d, J =8.1hz, 1h), 7.74 (dd, J =8.0,0.5hz, 1h), 7.43-7.38 (m, 1H), 7.36-7.24 (m, 6H), 4.59 (s, 2H), 3.87 (t, J =6.3hz, 2h), 3.61 (t, J =6.3hz, 2h), see fig. 1.
Comparative example 2
10.4g of the compound (III) (0.033mol, 1.0 eq), 1.1g of sodium tungstate (3.3 mmol, 0.1eq) and 100mL of ethanol were charged into a reaction flask, the temperature was raised to 70 to 80 ℃, 18.8g of hydrogen peroxide (0.166mol, 5.0 eq) was added dropwise to the reaction mixture, and the reaction was allowed to proceed for at least 2 hours under heat. After the reaction was completed, hot filtration, cooling filtration and drying were carried out to obtain 8.6g of compound (IV) as a white solid. The nuclear magnetic data are as follows: 1 H NMR(CDCl 3 400 MHz) delta 8.23-8.16 (m, 1H), 7.97-7.90 (m, 1H), 7.59 (dtd, J =15.2,7.3,1.2hz, 2h), 7.21-7.06 (m, 3H), 6.98 (d, J =7.0hz, 2h), 4.38 (s, 2H), 3.99 (t, J =5.8hz, 2h), 3.85 (t, J =5.8hz, 2h), see fig. 2.
Comparative example 3
10.4g of Compound (III) (0.033mol, 1.0eq), 50g of 1, 4-dioxane and 50g of hydroalcoholic were charged in a reaction flask, heated to 25 to 30 ℃ and 44.87g of potassium hydrogen peroxysulfate complex salt (Oxone) (0.073mol, 2.2eq) was charged in the reaction flask, and the mixture was allowed to react for at least 2 hours under heat. After the reaction, sodium thiosulfate was quenched, ethyl acetate was extracted, sodium chloride aqueous solution was extracted, rotary evaporation was performed under reduced pressure, and the distillate was recrystallized from ethanol to obtain 8.5g of compound (IV) as a white solid.
Example 1
100g of 2-mercaptobenzothiazole (I) (0.60mol, 1.05eq), 86.6g of potassium carbonate (0.63mol, 1.1eq) and 500mL of ethanol were charged in a reaction flask, and 122.0g of benzyl-2-bromoethyl ether (II) (0.57mol, 1eq) was added dropwise to the reaction solution at room temperature for at least 2 hours. After the reaction is finished, filtering to obtain an ethanol solution of the compound (III), and directly putting the ethanol solution into the next reaction.
Adding 19.7g of sodium tungstate (0.06mol, 0.1eq) into the reaction bottle of the whole batch of the ethanol solution of the compound (III), heating to 70-80 ℃, dropwise adding 403g of hydrogen peroxide (3.56mol, 6.3eq) into the reaction solution, and keeping the temperature for reaction for at least 2 hours. After the reaction, the mixture is filtered by heating, cooled to 0 to 10 ℃, filtered and dried to obtain 143.9g of white solid of the compound (IV), and the yield of the two-step reaction is 76%.
Example 2
Into a reaction flask were charged 100g of 2-mercaptobenzothiazole (I) (0.60mol, 1.05eq), 86.6g of potassium carbonate (0.63mol, 1.1eq) and 500mL of ethanol, and 122.0g of benzyl-2-bromoethyl ether (II) (0.57mol, 1eq) was added dropwise to the reaction solution and reacted for at least 2 hours. After the reaction is finished, filtering to obtain a compound (III) ethanol solution, and directly putting the compound (III) ethanol solution into the next reaction.
Adding 750mL of water into the reaction bottle of the whole batch of the ethanol solution of the compound (III), heating to 45-55 ℃, adding 716g of potassium hydrogen peroxysulfate composite salt (Oxone) (1.16mol, 2.05eq) into the reaction bottle in batches, and keeping the temperature for reaction for at least 4 hours. After the reaction is finished, cooling to 0-10 ℃ and filtering. The filter cake was dissolved with ethyl acetate, extracted with 10% sodium thiosulfate, rotary evaporated under reduced pressure, slurried with ethanol, filtered, and dried to give 156.1g of compound (IV) as a white solid with a purity of 99.4% and a two-step reaction yield of 82%.
Example 3
100g of Compound (IV) (0.3 mol, 1eq) and 800mL of ethanol were charged in a reaction flask, and 22.7g of sodium borohydride (0.6 mol, 2eq) was added to the reaction solution at room temperature to carry out a reaction for at least 1 hour. After the reaction was completed, rotary evaporation under reduced pressure was performed, methyl t-butyl ether was added to the mixture to make a slurry, which was filtered and dried to obtain 77.7g of compound (V) as a white solid with a purity of 99.3%, a yield of 97% and a total yield of 80%. The nuclear magnetic data are as follows: 1 H NMR(CD 3 OD,400 MHz) δ 7.37-7.21 (m, 5H), 4.51 (s, 2H), 3.77 (t, J =6.4hz, 2h), 2.53 (t, J =6.4hz, 2h), see fig. 3.
Comparative example 4
30g of compound (V) (0.135mol, 1eq) and 150g of water were charged in a reaction flask, and 19g of 39.5% aqueous calcium chloride solution (67.5mmol, 0.5eq) was charged in the reaction flask at room temperature, filtered by cooling, rinsed with water, and dried to obtain 13.7g of a white solid product of compound (VII) with a yield of 46%.
Example 4
70g of Compound (V) (0.315mol, 1eq), 350mL of water and 350mL of methyl t-butyl ether were charged into a reaction flask, and 31.9g of concentrated hydrochloric acid (0.315mol, 1eq) was charged into the reaction flask at room temperature, followed by acidification and extraction for separation. To the organic layer was added 11.2g of calcium hydroxide (0.15 mol,0.48 eq), filtered, the crude product is added with 90% ethanol for pulping, filtered and dried to obtain 57.0g of a white solid product of the compound (VII) with the purity of 99.9%, the yield of 79% and the total yield of 63%. The nuclear magnetic data are as follows: 1 H NMR(D 2 O,400MHz)δ7.54-7.30(m,5H),4.80(s,4H),4.54(s,2H),3.81(t,J＝6.1Hz,2H),2.59(t,J＝6.1Hz,2H)； 13 C NMR(D 2 o,100 MHz) δ 137.1,128.7,128.5,128.3,72.9,64.8,61.1, see fig. 4; mass Spectrometry [ C 18 H 23 CaO 6 S 2 ] + Calculated 439.06 and experimental 439.06.
Claims (9)
1. An aliphatic sulfinic acid calcium salt, which is characterized in that,
the structural formula of the aliphatic sulfinic acid calcium salt is as follows:
wherein, X is methylene or oxygen atom, and R is hydrogen, alkyl or benzyl.
2. The aliphatic sulfinic acid calcium salt according to claim 1, wherein X is an oxygen atom and R is benzyl.
3. Preparation of the aliphatic calcium sulfinate salt according to any of claims 1 or 2, comprising the following preparation steps:
step 1)
In the first step, aliphatic sulfinic acid sodium salt (V) is in acid to obtain a formula VI;
the acid is any one or more of inorganic acid and organic acid; wherein the inorganic acid is preferably hydrochloric acid, sulfuric acid, potassium bisulfate, sodium bisulfate; the organic acid is preferably trifluoroacetic acid, methanesulfonic acid and p-toluenesulfonic acid;
the solvent is an ether or ester or a solvent with the water content of toluene being less than 5%;
step 2)
Calcium ions are directly added to obtain an aliphatic sulfinic acid calcium salt (VII);
the calcium ions are derived from any one or more of calcium hydroxide, calcium oxide, calcium carbonate and calcium chloride;
the pulping solvent is alcohol or a mixture of alcohol and water;
4. the aliphatic sulfinic acid calcium salt according to claim 1, wherein the inorganic acid in step 1) is hydrochloric acid, and the molar ratio of the sulfinic acid sodium salt compound (V) to the hydrochloric acid reagent is 1.
5. The aliphatic sulfinic acid calcium salt according to claim 1, wherein the inorganic acid in step 1) is hydrochloric acid, the ethers are methyl tert-butyl ether and 2-methyl tetrahydrofuran, and the esters are any one or more of ethyl acetate, isopropyl acetate, n-butyl acetate and isobutyl acetate.
6. The aliphatic sulfinic acid calcium salt according to claim 1, wherein the calcium ion source in step 2) is preferably calcium hydroxide, and the molar ratio of sulfinic acid sodium salt compound (V) to calcium hydroxide reagent is 1.45-1.
7. The aliphatic sulfinic acid calcium salt according to claim 1, wherein the alcohol in step 2) is any one or more of methanol, ethanol and isopropanol.
8. The aliphatic sulfinic acid calcium salt according to claim 1, wherein the mass ratio of ethanol to water in step 2) is from 80 to 95.
9. The aliphatic sulfinic acid calcium salt according to claim 1, wherein the mass ratio of ethanol to water in step 2) is 80-95.
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