CN114874116A - Preparation method of thiosulfonate - Google Patents
Preparation method of thiosulfonate Download PDFInfo
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- CN114874116A CN114874116A CN202210617067.4A CN202210617067A CN114874116A CN 114874116 A CN114874116 A CN 114874116A CN 202210617067 A CN202210617067 A CN 202210617067A CN 114874116 A CN114874116 A CN 114874116A
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- GWIKYPMLNBTJHR-UHFFFAOYSA-M thiosulfonate group Chemical group S(=S)(=O)[O-] GWIKYPMLNBTJHR-UHFFFAOYSA-M 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- PRWATGACIORDEL-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=C(C#N)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C(N2C3=CC=CC=C3C3=CC=CC=C32)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C1C#N PRWATGACIORDEL-UHFFFAOYSA-N 0.000 claims description 2
- YCBWLMWEQURJHX-UHFFFAOYSA-N 4-(trifluoromethyl)cyclohexan-1-amine Chemical compound NC1CCC(C(F)(F)F)CC1 YCBWLMWEQURJHX-UHFFFAOYSA-N 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- WHELTKFSBJNBMQ-UHFFFAOYSA-L dichlororuthenium;2-pyridin-2-ylpyridine;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ru+2].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 WHELTKFSBJNBMQ-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000003321 amplification Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 50
- 150000001875 compounds Chemical class 0.000 description 34
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- -1 aryl diazonium salt Chemical class 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 238000002390 rotary evaporation Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- 239000012954 diazonium Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 5
- 239000012346 acetyl chloride Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- CHLCPTJLUJHDBO-UHFFFAOYSA-M sodium;benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=C1 CHLCPTJLUJHDBO-UHFFFAOYSA-M 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- IZDCAWCUMWJBLM-UHFFFAOYSA-M [K+].[O-]S(=O)=S Chemical compound [K+].[O-]S(=O)=S IZDCAWCUMWJBLM-UHFFFAOYSA-M 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 229960001948 caffeine Drugs 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- RYYVLZVUVIJVGH-UHFFFAOYSA-N trimethylxanthine Natural products CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/04—Thiosulfonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/69—Benzenesulfonamido-pyrimidines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of thiosulfonate, belonging to the technical field of organic compounds. The preparation method comprises the following steps: under the action of catalyst and additive
And
mixing, and reacting under the irradiation of ultraviolet light to obtain the thiosulfonic acid ester
The method has the advantages of simple and easily obtained raw materials, mild reaction conditions and environmental friendliness; and the operation steps are simple and convenient, the yield is high, the reaction conditions are suitable for amplification reaction, and a foundation is laid for industrial production.
Description
Technical Field
The invention belongs to the technical field of organic compounds, and particularly relates to a preparation method of thiosulfonate.
Background
The thiosulfonate is an important sulfur-containing organic compound, has obvious antiviral, antibacterial and bactericidal activities, and is widely applied to polymer production and agriculture. In addition, the thiosulfonate is a novel sulfur reagent, and has better stability and low toxicity compared with the traditional sulfur reagent
Synthesis of asymmetric thiosulfonates is more challenging than synthesis of symmetric thiosulfonates. The asymmetric thiosulfonate is generally synthesized by complexing potassium thiosulfonate with a halohydrocarbon or sulfurizing a disulfide with sodium sulfinate. However, these methods are often limited by the use of toxic or unstable reagents, additional oxidants, or low yields. There is thus a need to develop new efficient and versatile strategies for preparing a class of thiosulfonates.
Disclosure of Invention
In order to solve the technical problem, the invention provides a preparation method of thiosulfonate.
The invention aims to provide a preparation method of thiosulfonate, which comprises the following steps: under the action of catalyst and additive
Mixing, and reacting under the irradiation of ultraviolet light of 400nm-10nm to obtain the thiosulfonate
Wherein R is 1 、R 2 Independently selected from unsubstituted or substituted aryl groups, unsubstituted or substituted heterocyclic groups.
In one embodiment of the invention, the substitution in the substituted aryl group may be ortho, meta or para.
In one embodiment of the present invention, the substituted aryl or substituted heterocyclic group may be mono-or polysubstituted.
In one embodiment of the invention, the wavelength of the ultraviolet light is in the range of 400nm to 10 nm.
In one embodiment of the present invention, the substituent group in the substituted aryl group is one or more of alkyl, halogen and alkoxy.
In one embodiment of the invention, the heterocyclic group is selected from substituted phenyl, naphthyl, pyridine or thiophene.
In one embodiment of the present invention, the substituent group in the unsubstituted or substituted heterocyclic group is one or more of alkyl, halogen and alkoxy.
In one embodiment of the invention, the catalyst is selected from one or more of tris (2,2' -bipyridyl) ruthenium (ii) chloride hexahydrate, tris (2-phenylpyridine) iridium, acridine hydrochloride and 2,4,5, 6-tetrakis (9-carbazolyl) -isophthalonitrile.
In one embodiment of the invention, the additive is selected from one or more of potassium phosphate, cesium carbonate and sodium hydrogen phosphate.
In one embodiment of the invention, the solvent is selected from one or more of acetonitrile, methanol and ethyl acetate.
In one embodiment of the present invention, the reaction conditions are: reacting at 20-30 ℃ for 12-15 h.
In one embodiment of the invention, the
In a molar ratio of 1:1 to 1: 2.
In one embodiment of the invention, the catalyst is used in an amount of 4 mol% to 6 mol%.
In one embodiment of the invention, the additive is used in an amount of 4 mol% to 6 mol%.
In one embodiment of the present invention, a specific reaction scheme of the present invention:
compared with the prior art, the technical scheme of the invention has the following advantages:
the technical scheme of the invention takes the commercialized aryl diazonium salt as a raw material, is cheap and easy to obtain, greatly widens the substrate range of the thiosulfonate, and can synthesize the thiosulfonate compound which is difficult to obtain in the past. The method is novel by adopting polysulfide as a source of the sulfosulfonyl group.
The reaction mechanism of the invention is as follows:
drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is a nuclear magnetic hydrogen spectrum of Compound 03 of the present invention.
FIG. 2 is a nuclear magnetic hydrogen spectrum of Compound 04 of the present invention.
FIG. 3 is a nuclear magnetic hydrogen spectrum of Compound 05 of the present invention.
Detailed Description
The present invention is further described in conjunction with table 1 and the following examples, which are not intended to limit the invention, so that those skilled in the art may better understand the present invention and can practice it.
Table 1 Structure of the Compound and 1H NMR data
Example 1
This example illustrates a specific synthesis of compound 01 in table 1. Compound 01 can be synthesized by the following reaction steps:
(1): synthesis of intermediate (a-1)
Aniline (10mmol) dissolved in 4mL distilled water and 3.4mL 50% HBF 4 After cooling to 0 deg.C, sodium nitrite (0.69g in 1.5mL distilled water) was slowly added dropwise over 5min, stirred for 30min, filtered, the precipitate collected, and redissolved with acetone. Diethyl ether was added until the tetrafluoroborate diazonium salt precipitated, filtered, washed three times with 3 × 10mL of diethyl ether and dried under vacuum to give the corresponding intermediate (a-1).
(2): synthesis of intermediate (a-2)
Sodium benzenesulfinate (10g, 61mmol) and S 8 (1.95g, 61mmol) was dissolved in anhydrous pyridine (60mL) to give a yellow solution. The reaction was stirred under argon and after 1 hour a white suspension was obtained. Ether was added to the suspension and the reaction was filtered and washed with anhydrous ether to give PhSO as a white crystalline solid 2 SNa。
1.97g (10mmol) PhSO were added 2 SNa was dissolved in chloroform (10mL), and 0.5mL of acetyl chloride (7.2mmol) was slowly added thereto, followed by stirring at room temperature for 12 hours. After the reaction is finished, extracting with ethyl acetate and water, removing a water layer, drying with anhydrous sodium sulfate, removing an organic solvent by rotary evaporation, and purifying by column chromatography to obtain a light yellow solid, namely the corresponding intermediate (a-2).
(3): synthesis of Compound 01
In the glove box, 0 was weighed.0384g (0.2mmol) of the compound (a-1), 0.08g (0.4mmol) of the compound (a-2), Ru (bpy) 3 Cl 2 ·6H 2 O (5 mol%) and K 3 PO 4 (1eq.) to a dry 8mL reaction vial, 2mL of the MercN solvent was added, the reaction vial was capped, and the reaction was allowed to proceed at room temperature for 12 hours. After the reaction is finished, removing the organic solvent by rotary evaporation, and purifying by column chromatography to obtain a white solid product compound 01, wherein the reaction yield is 80 percent 1 The H NMR data are shown in Table 1.
Example 2
This example illustrates a specific synthetic method for compound 02 in table 1. Compound 02 can be synthesized by the following reaction steps:
(1): synthesis of intermediate (a-3)
Aniline (10mmol) dissolved in 4mL distilled water and 3.4mL 50% HBF 4 After cooling to 0 deg.C, sodium nitrite (0.69g in 1.5mL distilled water) was slowly added dropwise over 5min, stirred for 30min, filtered, the precipitate collected, and redissolved with acetone. Diethyl ether was added until the tetrafluoroborate diazonium salt precipitated, filtered, washed three times with 3 × 10mL of diethyl ether and dried under vacuum to give the corresponding intermediate (a-3).
(2): synthesis of intermediate (a-2)
Sodium benzenesulfinate (10g, 61mmol) and S 8 (1.95g, 61mmol) was dissolved in anhydrous pyridine (60mL) to give a yellow solution. The reaction was stirred under argon and after 1 hour a white suspension was obtained. Diethyl ether was added to the suspension, and the reaction was filtered and washed with anhydrous diethyl ether. PhSO as a white crystalline solid is obtained 2 SNa。
1.97g (10mmol) of PhSO 2 SNa was dissolved in chloroform (10mL), and 0.5mL of acetyl chloride (7.2mmol) was slowly added thereto, followed by stirring at room temperature for 12 hours. After the reaction is finished, extracting with ethyl acetate and water, removing a water layer, drying with anhydrous sodium sulfate, removing an organic solvent by rotary evaporation, and purifying by column chromatography to obtain a light yellow solid, namely the corresponding intermediate (a-2).
(3): synthesis of Compound 02
In a glove box, 0.0453g (0.2mmol) of Compound (a-1), 0.08g (0.4mmol) of Compound (a-2), Ru (bpy) 3 Cl 2 ·6H 2 O (5 mol%) and K 3 PO 4 (1eq.) to a dry 8mL reaction vial, 2mL of the MercN solvent was added, the reaction vial was capped, and the reaction was allowed to proceed at room temperature for 12 hours. After the reaction is finished, the organic solvent is removed by rotary evaporation, and a white solid product compound 02 is obtained after column chromatography purification, wherein the reaction yield is 85 percent 1 The HNMR data are shown in Table 1.
Example 3
This example illustrates a specific synthetic method for compound 03 in table 1. Compound 03 can be synthesized by the following reaction steps:
(1): synthesis of intermediate (a-4)
Aniline (10mmol) dissolved in 4mL distilled water and 3.4mL 50% HBF 4 After cooling to 0 deg.C, sodium nitrite (0.69g in 1.5mL distilled water) was slowly added dropwise over 5min, stirred for 30min, filtered, the precipitate collected, and redissolved with acetone. Diethyl ether was added until the tetrafluoroborate diazonium salt precipitated, filtered, washed three times with 3 × 10mL of diethyl ether and dried under vacuum to give the corresponding intermediate (a-3).
(2): synthesis of intermediate (a-2)
Sodium benzenesulfinate (10g, 61mmol) and sulfur (1.95g, 61mmol) were dissolved in anhydrous pyridine (60mL) to give a yellow solution. The reaction was stirred under argon and after 1 hour a white suspension was obtained. Ether was added to the suspension and the reaction was filtered and washed with anhydrous ether to give PhSO as a white crystalline solid 2 SNa。
1.97g (10mmol) PhSO were added 2 SNa was dissolved in chloroform (10mL), and 0.5mL of acetyl chloride (7.2mmol) was slowly added thereto, followed by stirring at room temperature for 12 hours. After the reaction is finished, extracting with ethyl acetate and water, removing a water layer, drying with anhydrous sodium sulfate, removing an organic solvent by rotary evaporation, and purifying by column chromatography to obtain a light yellow solid, namely the corresponding intermediate (a-2).
(3): synthesis of Compound 03
In a glove box, 0.0474g (0.2mmol) of Compound (a-4), 0.08g (0.4mmol) of Compound (a-2), Ru (bpy) 3 Cl 2 ·6H 2 O (5 mol%) and K 3 PO 4 (1eq.) to a dry 8mL reaction vial, 2mL of MeCN solvent was added, the reaction vial was capped, and the reaction was allowed to proceed at room temperature for 12 hours. After the reaction is finished, removing the organic solvent by rotary evaporation, and purifying by column chromatography to obtain a brown solid product compound 03 with the reaction yield of 94 percent 1 The H NMR data are shown in Table 1, and the nuclear magnetic spectrum is shown in FIG. 1.
Example 4
This example illustrates a specific synthetic method for compound 04 in table 1. Compound 04 can be synthesized by the following reaction steps:
(1): synthesis of intermediate (a-5)
In a 50mL round-bottom flask, heterocyclic amine (10.6mmol) was dissolved in absolute ethanol (8mL) and HBF 4 (50%, 4mL,32mmol) of the mixed solution, t-BuONO (6.5mL,48mmol) was slowly added dropwise at 0 ℃. Diethyl ether (4mL) was added without the diazonium salt precipitating. The mixture was filtered, washed with diethyl ether (10mL) and petroleum ether (10mL) and dried to give the desired heterocyclic diazonium salt (a-5).
(2): synthesis of intermediate (a-2)
Sodium benzenesulfinate (10g, 61mmol) and S 8 (1.95g, 61mmol) was dissolved in anhydrous pyridine (60mL) to give a yellow solution. The reaction was stirred under argon and after 1 hour a white suspension was obtained. Ether was added to the suspension and the reaction was filtered and washed with anhydrous ether to give PhSO as a white crystalline solid 2 SNa。
1.97g (10mmol) PhSO were added 2 SNa was dissolved in chloroform (10mL), and 0.5mL of acetyl chloride (7.2mmol) was slowly added thereto, followed by stirring at room temperature for 12 hours. After the reaction is finished, extracting with ethyl acetate and water, removing a water layer, drying with anhydrous sodium sulfate, removing an organic solvent by rotary evaporation, and purifying by column chromatography to obtain a light yellow solid, namely the corresponding intermediate (a-2).
(3): synthesis of Compound 04
In the glove box, 0.0464g (0) was weighed.2mmol) of the compound (a-4), 0.08g (0.4mmol) of the compound (a-2), Ru (bpy) 3 Cl 2 ·6H 2 O (5 mol%) and K 3 PO 4 (1eq.) to a dry 8mL reaction vial, 2mL of MeCN solvent was added, the reaction vial was capped, and the reaction was allowed to proceed at room temperature for 12 hours. And after the reaction is finished, removing the organic solvent by rotary evaporation, and purifying by column chromatography to obtain a white solid product. Namely the compound 04, the yield is 70 percent, 1 the HNMR data are shown in Table 1, and the nuclear magnetic spectrum is shown in FIG. 2.
Example 5
This example illustrates a specific synthetic method for compound 05 in table 1, compound 05 can be synthesized by the following reaction steps:
(1): synthesis of intermediate (a-6)
In a 50mL round-bottom flask, the amine (10mmol) was dissolved in absolute ethanol (3mL) and HBF 4 (50%, 2.5mL,20mmol) of the mixed solution, t-BuONO (6.5mL,48mmol) was slowly added dropwise at 0 deg.C, the reaction was stirred at room temperature for 1h, and 20mL of diethyl ether was added to precipitate the diazonium salt. The mixture was filtered and washed with 3X 10mL of diethyl ether. Drying in vacuum to obtain the small molecule diazonium salt (a-6) of the required medicine.
(2): synthesis of intermediate (a-2)
Sodium benzenesulfinate (10g, 61mmol) and S 8 (1.95g, 61mmol) was dissolved in anhydrous pyridine (60mL) to give a yellow solution. The reaction was stirred under argon and after 1 hour a white suspension was obtained. Ether was added to the suspension and the reaction was filtered and washed with anhydrous ether to give PhSO as a white crystalline solid 2 SNa。
1.97g (10mmol) PhSO were added 2 SNa was dissolved in chloroform (10mL), and 0.5mL of acetyl chloride (7.2mmol) was slowly added thereto, followed by stirring at room temperature for 12 hours. After the reaction is finished, extracting with ethyl acetate and water, removing a water layer, drying with anhydrous sodium sulfate, removing an organic solvent by rotary evaporation, and purifying by column chromatography to obtain a light yellow solid, namely the corresponding intermediate (a-2).
(3): synthesis of Compound 05
In a glove box, 0.0754g (0.2mmol) of the compound (a-4), 0.08g (0.4mmol) of the compound (a-2), Ru (bpy) 3 Cl 2 ·6H 2 O (5 mol%) and K 3 PO 4 (1eq.) to a dry 8mL reaction vial, 2mL of MeCN solvent was added, the reaction vial was capped, and the reaction was allowed to proceed at room temperature under light for 12 hours. After the reaction is finished, the organic solvent is removed by rotary evaporation, and a yellow solid product, namely the compound 03 is obtained after column chromatography purification, wherein the reaction yield is 74 percent 1 The H NMR data are shown in Table 1, and the nuclear magnetic spectrum is shown in FIG. 3.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A preparation method of thiosulfonate is characterized by comprising the following steps: under the action of catalyst and additive
Mixing, and reacting under the irradiation of ultraviolet light to obtain the thiosulfonic acid ester
Wherein R is 1 、R 2 Independently selected from unsubstituted or substituted aryl groups, unsubstituted or substituted heterocyclic groups.
2. The method according to claim 1, wherein the substituent group in the substituted aryl group is one or more of an alkyl group, a halogen group and an alkoxy group.
3. The method of claim 1, wherein the heterocyclic group is selected from the group consisting of substituted phenyl, naphthyl, pyridine, and thiophene.
4. The method according to claim 1, wherein the substituent group in the unsubstituted or substituted heterocyclic group is one or more of an alkyl group, a halogen group and an alkoxy group.
5. The method according to claim 1, wherein the catalyst is one or more selected from the group consisting of tris (2,2' -bipyridyl) ruthenium (II) chloride hexahydrate, tris (2-phenylpyridine) iridium, acridine hydrochloride, and 2,4,5, 6-tetrakis (9-carbazolyl) -isophthalonitrile.
6. The method of claim 1, wherein the additive is selected from one or more of potassium phosphate, cesium carbonate, and sodium hydrogen phosphate.
7. The method according to claim 1, wherein the solvent is one or more selected from acetonitrile, methanol, and ethyl acetate.
8. The method of claim 1, wherein the reaction conditions are: reacting at 20-30 ℃ for 12-15 h.
9. According to the rightThe method according to claim 1, wherein the method comprises
In a molar ratio of 1:1 to 1: 2.
10. The preparation method according to claim 1, wherein the amount of the catalyst is 4 mol% to 6 mol%; the dosage of the additive is 4 mol% -6 mol%.
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