CN115385831A - Method for preparing alkyne sulfone compound by oxidation of selenium-containing catalytic system - Google Patents
Method for preparing alkyne sulfone compound by oxidation of selenium-containing catalytic system Download PDFInfo
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- -1 alkyne sulfone compound Chemical class 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 25
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title abstract description 5
- 229910052711 selenium Inorganic materials 0.000 title abstract description 5
- 239000011669 selenium Substances 0.000 title abstract description 5
- 230000003647 oxidation Effects 0.000 title description 5
- 238000007254 oxidation reaction Methods 0.000 title description 5
- 230000003197 catalytic effect Effects 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 51
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 21
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- YWWZCHLUQSHMCL-UHFFFAOYSA-N diphenyl diselenide Chemical compound C=1C=CC=CC=1[Se][Se]C1=CC=CC=C1 YWWZCHLUQSHMCL-UHFFFAOYSA-N 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 241000872931 Myoporum sandwicense Species 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052736 halogen Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract description 10
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 abstract description 4
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 16
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 13
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 5
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon 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
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/06—Separation; Purification; Stabilisation; Use of additives
-
- 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 for oxidizing alkyne sulfur compounds into alkyne sulfone compounds with selenium participation, which has the advantages of simple operation process, high selectivity, yield of 95 percent or more, simple subsequent treatment and capability of obtaining pure products without complex separation and purification. Compared with the traditional method, the method takes water as a solvent, and uses sodium periodate to oxidize cheap ruthenium carbon to generate ruthenium tetroxide at normal temperature, thereby further oxidizing the alkyne-sulfur compound to synthesize the alkyne-sulfone compound. Therefore, the method is more efficient, rapid, environment-friendly and mild.
Description
(I) technical field
The invention relates to an oxidation synthesis method of selenium-participated alkyne sulfone compounds.
(II) background of the invention
The alkynyl sulfone is a sulfone derivative with important synthesis application, and the excellent reaction activity is represented by a carbon-carbon triple bond, and a series of reactions such as addition, substitution, cyclization and the like can be carried out on the triple bond. Due to the special structure that alkynyl is connected with sulfonyl, the alkyne sulfone compound can be directly used as antibiotic or anticancer drug.
The synthesis method of the alkyne sulfone compound mainly comprises a elimination method, a substitution method, an oxidation method and the like. Nair et al, which uses aryl acetylene and arylsulfinate as raw materials, first produce an intermediate, alkene sulfone, under anhydrous and anaerobic conditions, catalyzed by a catalyst CAN, and then add potassium carbonate to reflux to obtain an alkyne sulfone product. The method has harsh conditions and expensive catalyst, and is easy to generate aryl acetylene coupling byproducts. Truce et al (1956) and Kabanya et al (1956) use alkynyl sulfur as raw material, and hydrogen peroxide and potassium hydrogen persulfate as oxidant respectively to obtain alkyne sulfur product, and both methods have low selectivity, and can obtain a part of sulfoxide product besides sulfone product.
At present, it is necessary to find a method for synthesizing the alkyne sulfone compound, which is green, high in selectivity, low in cost, simple in treatment and easy to operate.
Disclosure of the invention
In order to solve the defects in the prior art, the invention provides a method for synthesizing the alkyne sulfone compound by catalyzing selenium at room temperature and catalyzing alkyne sulfur by using cheap ruthenium carbon as a catalyst, and the method has the advantages of greenness, low price, high selectivity, simple post-treatment and the like.
The technical scheme of the invention is as follows:
a synthetic method of a alkyne sulfone compound shown as a formula (II) specifically comprises the following steps:
a compound shown as a formula (I) is taken as a reaction raw material, ru/C is taken as a catalyst, and NaIO is carried out in the presence of diphenyl diselenide 4 The method comprises the following steps of (1) taking an oxidant, water, acetonitrile or a mixed solution of the water and the acetonitrile as a solvent (preferably a mixed solution of the acetonitrile and the water with a volume ratio of 1:3), reacting at room temperature (20-30 ℃), and after the reaction is finished, carrying out aftertreatment on the obtained reaction liquid to obtain the alkyne sulfone compound shown in the formula (II); the dosage of the Ru/C is calculated by the substance amount of Ru, the compound shown as the formula (I) and NaIO 4 Ru/C and diphenyl diselenide in a mass ratio of 1:0.5-5: 0.005-0.02: 0.005 to 0.02 (preferably 1;
in the formulae (I) and (II), R1 is phenyl or C 1～7 Alkyl or halogen substituted phenyl or C 3～8 R2 is C 1～10 Alkyl, phenyl or by C 1～7 Alkyl or halogen substituted phenyl.
Preferably, R1 is phenyl, 4-fluorophenyl and n-butyl; r2 is methyl, ethyl or propyl.
Further preferably, in an embodiment of the present invention, the alkyne sulfone compound represented by formula II is one of the following:
preferably, the mass fraction of the active ingredient Ru in the Ru/C is 5%.
Ru/C (5% (g/g) of Ru) is used in an amount of 0.5 to 2% (preferably 1%) of the amount of the substance of the compound represented by formula (I) based on the amount of the substance of Ru, and diphenyldiselenide is used in an amount of 0.5 to 2mol% (preferably 1 mol%).
The progress of the reaction of the present invention can be monitored by GC-MS, and the completion of the reaction of the compound (I) is regarded as a time point for judging the completion of the reaction, and the reaction time is usually 1 to 2 hours.
Further, the post-treatment of the invention is as follows: and (3) filtering the reaction solution by using kieselguhr, washing the obtained filtrate by using dichloromethane, combining washing solutions, washing the washing solutions by using a saturated sodium chloride aqueous solution (twice), removing water by using anhydrous sodium sulfate, removing the solvent in vacuum, and drying to obtain the alkyne sulfone compound shown in the formula (II).
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a preparation method for oxidizing an alkyne sulfur compound into an alkyne sulfone compound with participation of selenium, which has the advantages of simple operation process, high selectivity, yield of 95 percent or more, simple subsequent treatment and capability of obtaining a pure product without complex separation and purification.
(2) The traditional method utilizes ruthenium tetroxide for oxidation, however, ruthenium tetroxide has the defects of unstable property, high toxicity, high price and the like, and has certain limitation; compared with the traditional method, the method takes water as a solvent, and uses sodium periodate to oxidize cheap ruthenium carbon to generate ruthenium tetroxide at normal temperature, so as to further oxidize the alkyne sulfur compound to synthesize the alkyne sulfone compound. Therefore, the method is more efficient, rapid, environment-friendly and mild.
(IV) detailed description of the preferred embodiment
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1: preparation of alkyne sulfone compound II-1
5mg (0.0025 mmol in terms of Ru) of a Ru/C catalyst (5% (g/g) Ru, K0803 from Kanna New materials, inc.) and 118mg (0.55 mmol) sodium periodate were added to the reaction flask, 1.5mL of water were added, 74mg (0.5 mmol) of I-1 were added to the reaction flask with stirring, stirring was continued at room temperature, and the reaction was monitored by GC-MS. After eight hours of reaction, the reaction solution was filtered through celite, and then the filtrate was washed with dichloromethane (10 ml x 2), and the washing solution was washed again with a saturated sodium chloride solution. Anhydrous sodium sulfate is used for removing water, the solvent is evaporated and dried to obtain a compound II-1 18mg, and the yield is 20%. Purity by HPLC 98%.
Example 2: preparation of alkyne sulfone compound II-1
10mg (0.005 mmol in terms of Ru) of a Ru/C catalyst (5% (g/g) in terms of Ru, K0803 from Corner New Material Ltd., K0803) and 160mg (0.75 mmol) of sodium periodate were charged into a reaction flask, 1.5mL of water was added, 74mg (0.5 mmol) of I-1 was charged into the reaction flask under stirring, stirring was continued at room temperature, the reaction was monitored by GC-MS, the reaction solution was filtered with celite after eight hours of reaction, and then the filtrate was washed with dichloromethane (10 mLx 2) and the washing solution was washed again with a saturated sodium chloride solution. Anhydrous sodium sulfate is used for removing water, the solvent is evaporated and dried to obtain the compound II-125.2 mg with the yield of 28%. Purity by HPLC was 97.3%. .
Example 3: preparation of alkyne sulfone compound II-1
10mg (0.005 mmol in terms of Ru) of a Ru/C catalyst (5% (g/g) in terms of Ru, K0803 from Corner New Material Ltd., K0803) and 160mg (0.75 mmol) of sodium periodate were charged into a reaction flask, 0.5mL of acetonitrile and 1.5mL of water were further added, 74mg (0.5 mmol) of I-1 were charged into the reaction flask under stirring, stirring was continued at room temperature, the reaction was monitored by GC-MS, the reaction solution was filtered with celite after eight hours of reaction, and then the filtrate was washed with dichloromethane (10 mLx 2) and the washing solution was washed again with a saturated sodium chloride solution. Anhydrous sodium sulfate is used for removing water, the solvent is evaporated and dried to obtain the compound II-1.5mg with the yield of 28 percent. Purity by HPLC was 97.3%.
Example 4: preparation of alkyne sulfone compound II-1
To a reaction flask, 10mg (0.005 mmol in terms of Ru) of Ru/C catalyst (5% (g/g) in terms of Ru, K0803 from Corner Material Ltd., K.sub.t.), 320mg (1.5 mmol) of sodium periodate, 1.56mg (0.005 mmol) of diphenyldiselenide, 0.5mL of acetonitrile and 1.5mL of water were added, 74mg (0.5 mmol) of I-1 was added to the reaction flask with stirring, and stirring was continued at room temperature for 1-2 hours. The reaction was monitored by GC-MS and stopped after completion of the reaction for I-1. The reaction solution was filtered through celite, after which the filtrate was washed with dichloromethane (10 mLx 2), and the washing solution was washed again with a saturated sodium chloride solution. Anhydrous sodium sulfate is used for removing water, the solvent is evaporated and dried to obtain the compound II-1.4mg with the yield of 96 percent. Purity by HPLC 98.3%. The structure of compound II-1 is characterized as follows:
1 H NMR(500MHz,CDCl 3 )δ7.62-7.59(m,2H),7.55-7.51(m,1H)，7.45-7.41(m,2H),3.32(s,3H)； 13 C NMR(126MHz,CDCl 3 )δ132.86,131.77,128.81,117.50,91.55,84.47,46.84；GC-MS(EI):m/z 180.02[M + ].
example 5: preparation of alkyne sulfone compound II-2
To a reaction flask, 10mg (0.005 mmol in terms of Ru) of Ru/C catalyst (5% (g/g) in terms of Ru, K0803 from Corner Material Ltd., K.sub.t.), 320mg (1.5 mmol) of sodium periodate, 1.56mg (0.005 mmol) of diphenyldiselenide, 0.5mL of acetonitrile and 1.5mL of water were added, 81mg (0.5 mmol) of I-2 was added to the reaction flask under stirring, and stirring was continued at room temperature for 1-2 hours. The reaction was monitored by GC-MS and stopped after the reaction of I-2 was complete. The reaction solution was filtered through celite, after which the filtrate was washed with dichloromethane (10 mLx 2), and the washing solution was washed again with a saturated sodium chloride solution. Anhydrous sodium sulfate to remove water, evaporating the solvent to dryness and drying to obtain a compound II-2.2mg with the yield of 95%. Purity by HPLC was 97.1%. The structure of compound II-2 is characterized as follows:
1 H NMR(500MHz,CDCl 3 )δ7.61(dd,J＝8.3,1.3Hz,2H),7.57–7.50(m,1H),7.47–7.41(m,2H),3.32(q,J＝7.4Hz,2H),1.56(t,J＝7.4Hz,3H).GC-MS(EI):m/z194.04[M + ].
example 6: preparation of alkyne sulfone compound II-3
10mg (0.005 mmol in terms of Ru) of Ru/C catalyst (5% (g/g) in Ru, K0803 from Kanna New materials, inc.), 320mg (1.5 mmol) of sodium periodate, 1.56mg (0.005 mmol) of diphenyldiselenide, 0.5mL of acetonitrile and 1.5mL of water were added to the reaction flask, 83mg (0.5 mmol) of I-3 were added to the reaction flask with stirring, and stirring was continued at room temperature for 1-2h. The reaction was monitored by GC-MS and stopped after the reaction of I-3 was complete. The reaction solution was filtered through celite, after which the filtrate was washed with dichloromethane (10 mLx 2), and the washing solution was washed again with a saturated sodium chloride solution. Anhydrous sodium sulfate to remove water, evaporating the solvent to dryness and drying to obtain a compound II-3.0mg with the yield of 95%. Purity by HPLC 98.9%. The structure of compound II-3 is characterized as follows:
1 H NMR(500MHz,CDCl 3 )δ7.66-7.59(m,2H),7.17-7.12(m,2H),3.31(s,3H)； 13 C NMR(126MHz,CDCl 3 )δ165.55,135.31,116.59,116.41,90.47,84.45,46.79；GC-MS(EI):m/z 198.02[M + ].
example 7: preparation of alkyne sulfone compound II-4
To a reaction flask, 10mg (0.005 mmol in terms of Ru) of Ru/C catalyst (5% (g/g) in terms of Ru, K0803 from Corner Material Ltd., K.sub.t.), 320mg (1.5 mmol) of sodium periodate, 1.56mg (0.005 mmol) of diphenyldiselenide, 0.5mL of acetonitrile and 1.5mL of water were added, and 64mg (0.5 mmol) of I-4 was added to the reaction flask under stirring, and stirring was continued at room temperature for 1-2 hours. The reaction was monitored by GC-MS and stopped after the reaction of I-4 was complete. The reaction solution was filtered through celite, after which the filtrate was washed with dichloromethane (10 mLx 2), and the washings were washed again with saturated sodium chloride solution. Anhydrous sodium sulfate is used for removing water, the solvent is evaporated and dried to obtain the compound II-4.4mg with the yield of 96 percent. Purity by HPLC 98.3%. The structure of compound II-4 is characterized as follows:
1 H NMR(500MHz,CDCl3)δ3.18(s,3H),2.41(t,J＝7Hz,2H),1.67-1.53(m,2H),1.53-1.32(m,2H),0.93(t,J＝7Hz,3H)； 13 C NMR(126MHz,CDCl 3 )δ95.8,77.4,46.8,29.1,22.1,18.6,13.5；GC-MS(EI):m/z 160.06[M + ].
example 8: preparation of alkyne sulfone compound II-5
To a reaction flask, 10mg (0.005 mmol in terms of Ru) of Ru/C catalyst (5% (g/g) in terms of Ru, K0803 from Corner Material Ltd., K.sub.t.), 320mg (1.5 mmol) of sodium periodate, 1.56mg (0.005 mmol) of diphenyldiselenide, 0.5mL of acetonitrile and 1.5mL of water were added, 119mg (0.5 mmol) of I-5 was added to the reaction flask with stirring, and stirring was continued at room temperature for 1-2 hours. The reaction was monitored by GC-MS and stopped after completion of the reaction of I-5. The reaction solution was filtered through celite, after which the filtrate was washed with dichloromethane (10 mLx 2), and the washing solution was washed again with a saturated sodium chloride solution. Anhydrous sodium sulfate is used for removing water, the solvent is evaporated and dried to obtain a compound II-5.3mg, and the yield is 95%. Purity by HPLC was 97.2%. The structure of compound II-5 is characterized as follows:
1 H NMR(500MHz,CDCl 3 )δ7.95(d,J＝8.3Hz,2H),7.40(d,J＝8.2Hz,2H),7.38(d,J＝8.3Hz,2H),7.16(d,J＝8.1Hz,2H),2.46(s,3H),2.36(s,3H). 13 C NMR(126MHz,CDCl 3 )δ145.3,142.4,139.1,132.7,130.0,129.5,127.5,114.9,93.7,85.2,21.8,21.7.
Claims (5)
1. the synthesis method of the alkyne sulfone compound shown in the formula (II) is characterized by comprising the following steps:
the compound shown in formula (I) is used as a reaction raw material, ru/C is used as a catalyst, naIO is added in the presence of diphenyl diselenide 4 The method comprises the following steps of (1) taking an oxidant, water, acetonitrile or a mixed solution of the water and the acetonitrile as a solvent, reacting at room temperature, and after the reaction is finished, carrying out post-treatment on the obtained reaction liquid to obtain the alkyne sulfone compound shown in the formula (II); the dosage of the Ru/C is calculated by the mass of Ru, the compound shown as the formula (I) and NaIO 4 And the mass ratio of Ru/C to diphenyl diselenide is 1:0.5-5: 0.005-0.02: 0.005-0.02;
in the formulae (I) and (II), R1 is phenyl or C 1～7 Alkyl or halogen substituted phenyl or C 3～8 R2 is C 1～10 Alkyl, phenyl or by C 1～7 Alkyl or halogen substituted phenyl.
2. The method for synthesizing the alkyne sulfone compound shown as the formula (II) in claim 1, wherein R1 is phenyl, 4-fluorophenyl or n-butyl; r2 is methyl, ethyl or propyl.
3. The method for synthesizing the alkyne sulfone compound shown as the formula (II) in claim 1, wherein the alkyne sulfone compound is one of the following compounds:
4. the method for synthesizing the alkyne sulfone compound shown as the formula (II) according to claim 1, which comprises the following steps: the mass fraction of an active ingredient Ru in the Ru/C is 5%.
5. The method for synthesizing the alkyne sulfone compound of formula (ii) as claimed in claim 1, wherein the post-treatment comprises: and (3) filtering the reaction solution by using kieselguhr, washing the obtained filtrate by using dichloromethane, combining washing solutions, washing by using a saturated sodium chloride aqueous solution, removing water by using anhydrous sodium sulfate, removing the solvent in vacuum, and drying to obtain the alkyne sulfone compound shown in the formula (II).
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3772023A (en) * | 1970-06-20 | 1973-11-13 | Konishiroku Photo Ind | Silver halide photographic element containing an acetylene sulfonyl compound as hardener |
| CN106565553A (en) * | 2016-09-28 | 2017-04-19 | 南方医科大学 | Synthetic method of alkynyl sulfone derivative |
| CN108484456A (en) * | 2018-02-01 | 2018-09-04 | 浙江工业大学 | A kind of method of selectively oxidizing sulfur ether |
| CN110642766A (en) * | 2019-08-30 | 2020-01-03 | 浙江工业大学 | Monoamine oxidase A inhibitor |
| CN110655480A (en) * | 2019-08-30 | 2020-01-07 | 浙江工业大学 | Synthetic method of sulfone compound |
| CN111139494A (en) * | 2020-01-09 | 2020-05-12 | 广西师范大学 | Method for synthesizing alkyne sulfone compound from terminal alkyne and sulfonyl hydrazide |
| CN111777534A (en) * | 2020-07-30 | 2020-10-16 | 南京林业大学 | Alkynyl sulfone compound and preparation method and application thereof |
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2022
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3772023A (en) * | 1970-06-20 | 1973-11-13 | Konishiroku Photo Ind | Silver halide photographic element containing an acetylene sulfonyl compound as hardener |
| CN106565553A (en) * | 2016-09-28 | 2017-04-19 | 南方医科大学 | Synthetic method of alkynyl sulfone derivative |
| CN108484456A (en) * | 2018-02-01 | 2018-09-04 | 浙江工业大学 | A kind of method of selectively oxidizing sulfur ether |
| CN110642766A (en) * | 2019-08-30 | 2020-01-03 | 浙江工业大学 | Monoamine oxidase A inhibitor |
| CN110655480A (en) * | 2019-08-30 | 2020-01-07 | 浙江工业大学 | Synthetic method of sulfone compound |
| CN111139494A (en) * | 2020-01-09 | 2020-05-12 | 广西师范大学 | Method for synthesizing alkyne sulfone compound from terminal alkyne and sulfonyl hydrazide |
| CN111777534A (en) * | 2020-07-30 | 2020-10-16 | 南京林业大学 | Alkynyl sulfone compound and preparation method and application thereof |
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