CN110872249B - Synthetic method of alpha, beta-tricarbonyl sulfur ylide compound - Google Patents
Synthetic method of alpha, beta-tricarbonyl sulfur ylide compound Download PDFInfo
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Abstract
The invention relates to a synthesis method of an alpha, beta-tricarbonyl sulfur ylide compound, which is characterized in that sulfur oxide ylide shown in a formula I is used as a raw material in an organic solvent, R in the formula I is selected from substituted or unsubstituted alkyl, C6-10 aryl or C4-10 heterocycle under the action of a catalyst, a substituent comprises alkyl, alkoxy, cyano, nitro and halogen, and the alkyl or alkoxy is substituted by 0, 1 or more halogen atoms;
Description
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to an alpha, beta-tricarbonyl sulfur ylide compound and a synthesis method thereof.
Background
Thiobeteride, a zwitterionic compound, has a structure of an adjacent carbanion stabilized by a sulfur cation and can be considered as a nucleophile with a leaving group. Therefore, the thioylide serving as a classical one-carbon synthon can be applied to the efficient synthesis of small-ring compounds such as epoxy, aziridine, cyclopropane and the like through the reaction with an electron-deficient pi system.
At present, toxic and harmful substances such as mercury, nitric acid and the like are generally needed for synthesizing the tetraone compound, so that a green and efficient mode or a reaction intermediate needs to be researched to solve the problems.
Disclosure of Invention
Based on the problems, the invention provides a synthesis method of an alpha, beta-tricarbonyl sulfur ylide compound, which is characterized in that the synthesis method comprises the steps of taking sulfur oxide ylide shown in a formula I as a raw material in an organic solvent, and reacting under the action of a catalyst; wherein, R in the formula I is selected from substituted or unsubstituted alkyl, C6-10 aryl or C4-10 heterocycle, the substituent comprises alkyl, alkoxy, cyano, nitro and halogen, and the alkyl or alkoxy is substituted by 0, 1 or more halogen atoms;
in one embodiment, the R comprises any one of the following groups:
in one embodiment, the catalyst comprises: anhydrous copper acetate and/or silver trifluoroacetate; the organic solvent comprises 1, 4-dioxane.
In one embodiment, the reaction temperature is 70-110 ℃, the reaction time is 8-14 h, and the reaction atmosphere is oxygen; after the reaction, the product is purified by silica gel column chromatography separation.
The purification method comprises the following steps: and after the reaction is finished, adding column chromatography silica gel, distilling under reduced pressure to remove the solvent, drying until the silica gel adsorbs the product powder, loading the product powder on a column, eluting and collecting by using a mixed solution of petroleum ether and ethyl acetate, and concentrating under reduced pressure to obtain the alpha, beta-tricarbonyl thioylide compound.
In one embodiment, the ratio of the amount of sulfur oxide ylide to the amount of catalyst material is 1 (0.1 to 0.2); the amount of the organic solvent added is 4-8 mL/mmol based on the amount of the sulfur oxide ylide substance represented by formula I.
It is another object of the present invention to provide an α, α, β -tricarbonylthioylide compound prepared according to the above synthesis method, the α, α, β -tricarbonylthioylide compound having the structure of formula ii:
wherein, R in the formula I is selected from substituted or unsubstituted alkyl, C6-10 aryl or C4-10 heterocycle, the substituent comprises alkyl, alkoxy, cyano, nitro and halogen, and the alkyl or alkoxy is substituted by 0, 1 or more halogen atoms.
In one embodiment, the R comprises the following groups:
has the advantages that:
the invention discloses a synthetic method of an alpha, beta-tricarbonyl sulfur ylide compound, which has the advantages of cheap and easily-synthesized raw materials, cheap and easily-obtained catalyst, high efficiency, greenness, wide substrate range, good electron withdrawing and electron donating group tolerance, synthesis of a heterocyclic substituent and a sulfur ylide of an alkane substituent, highest yield up to 82 percent and simple operation.
And provides an alpha, beta-tricarbonyl sulfur ylide compound which can be further reacted to generate a tetraone compound, such as DPBT, and the compound usually needs mercury, nitric acid and other toxic and harmful substances for synthesis. And three carbonyl groups can be used as sites for further reactions.
Drawings
FIG. 1 is a single crystal structural diagram of an α, α, β -tricarbonylthioylide compound prepared in example 1.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the following specific examples.
The starting sulfur oxide ylide used in the present invention can be prepared on its own in accordance with the existing literature, for example the literature y.yuan, x. -f.wu, org.lett.2019,21,5310. The invention provides a synthesis method which comprises the following steps:
to THF (30mL) in which potassium tert-butoxide (3.0g, 27.2mmol) was dissolved under argon at room temperature was added trimethyl sulfoxide iodide (5.0g, 20.6mmol), and the mixture was dissolved with stirring and refluxed for 2 hours. The reaction mixture was then cooled to 0 ℃ and acid chloride (7.0mmol) was added. Warm to room temperature and stir overnight. After completion of the reaction, the solvent was distilled off under reduced pressure, and 15ml of water was added to conduct extraction with ethyl acetate (3X 50 ml). The organic solution is treated with anhydrous Na2SO4Drying, adding 100-mesh and 200-mesh column chromatography silica gel, distilling under reduced pressure to remove the solvent, performing silica gel column chromatography separation on the crude product, eluting with ethyl acetate, performing TLC elution tracking detection, collecting eluent containing the target product, combining the target product eluent, and concentrating under reduced pressure to obtain the sulfur oxide ylide compound shown in the formula I.
The synthetic route is as follows:
in some embodiments of the invention:
in example 1R is
In example 2R is
In example 3R is
In example 4R is
In example 5R is
In example 6R is
In example 7R is
In example 8R is
In example 9R is
In example 10R is
In example 11R is
In example 12R is
In example 13R is
The raw material acid chloride with a substituent used in the present invention can be purchased commercially for use.
Example 1
This example prepares α, α, β -tricarbonylthioylide compounds having the following structural formula:
the preparation method comprises the following steps: to a 25ml schlenk tube equipped with a magnetic stirrer was added sulfur oxide ylide (0.4mmol, 78.4mg), Cu (OAc)2(0.04mmol，7.2mg)、CF3COOAg (0.04mmol, 8.8 mg). The reaction tube was replaced with oxygen three times under reduced pressure. After addition of 2ml of anhydrous 1, 4-dioxane, the reaction was stirred at 90 ℃ for 12 hours. After the reaction is finished, adding 200-mesh column chromatography silica gel, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the crude product, eluting with mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate: 1:2), carrying out TLC (thin layer chromatography) elution tracking detection, collecting eluent containing a target product, combining the target product eluent, and concentrating under reduced pressure to obtain the alpha, beta-tricarbonyl thioylide compound shown in the formula III-1 with the yield of 81%. The material was a white solid with a melting point of 234.6-235.8 ℃. An X-ray diffraction tester is adopted to test the single crystal structure of the alpha, beta-tricarbonyl sulfur ylide compound to obtain a structure analysis chart as shown in figure 1.
Characterization data: 1H NMR (400MHz, CDCl)3)δ7.80-7.73(m,2H),7.55-7.47(m,3H),7.38(t,J＝7.7Hz,2H),7.35-7.29(m,1H),7.18(t,J＝7.7Hz,2H),3.78(s,6H).13C NMR(101MHz,DMSO-d6)δ191.9,189.2,186.3,140.9,134.0,133.9,131.8,129.5,129.1,128.9,128.2,102.3,42.0.HRMS m/z(ESI)calcd for C18H16O4S(M+H)+329.08421,found 329.08435.
Example 2
This example prepares α, α, β -tricarbonylthioylide compounds having the following structural formula:
the preparation method comprises the following steps: to a 25ml schlenk tube equipped with a magnetic stirrer was added 4-methylphenylsulfoxide ylide (0.4mmol, 84mg), Cu (OAc)2(0.04mmol，7.2mg)、CF3COOAg (0.04mmol, 8.8 mg). The reaction tube was replaced with oxygen three times under reduced pressure. After addition of 2ml of anhydrous 1, 4-dioxane, the reaction was stirred at 90 ℃ for 12 hours. After the reaction is finished, adding 200-mesh column chromatography silica gel, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the crude product, eluting with mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate: 1), carrying out TLC (thin layer chromatography) elution tracking detection, collecting eluent containing a target product, combining the target product eluent, and concentrating under reduced pressure to obtain the alpha, beta-tricarbonyl thioylide compound shown in the formula III-2 with the yield of 81%. This material was a white solid with a melting point of 203.0-204.2 ℃.
Characterization data:1H NMR(400MHz,CDCl3)δ7.65(d,J＝8.1Hz,2H),7.41(d,J＝8.0Hz,2H),7.18(d,J＝7.9Hz,2H),6.98(d,J＝7.8Hz,2H),3.74(s,6H),2.39(s,3H),2.27(s,3H).13C NMR(101MHz,CDCl3)δ191.9,189.9,186.2,144.6,142.3,137.2,131.0,129.5,129.1,129.0,128.5,99.5,43.5,21.8,21.5.HRMS m/z(ESI)calcd for C20H20O4S(M+H)+357.11551,found 357.11542.
example 3
This example prepares α, α, β -tricarbonylthioylide compounds having the following structural formula:
the preparation method comprises the following steps: to a 25ml schlenk tube equipped with a magnetic stirrer was added 4-fluorophenylthioylide (0.4mmol, 85.6mg), Cu (OAc)2(0.04mmol，7.2mg)、CF3COOAg (0.04mmol, 8.8 mg). The reaction tube was replaced with oxygen three times under reduced pressure. After addition of 2ml of anhydrous 1, 4-dioxane, the reaction was stirred at 90 ℃ for 12 hours. After the reaction is finished, 200 meshes of column chromatography silica gel is added, the solvent is removed by reduced pressure distillation, the crude product is subjected to silica gel column chromatography separation, and is eluted by mixed liquid of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate: 1:2), TLC elution tracking detection is carried out, eluent containing a target product is collected, the target product eluent is combined, and the alpha, beta-tricarbonyl sulfur ylide compound shown in the formula III-3 is obtained by reduced pressure concentration, wherein the yield is 73%. The material is a white solid with a melting point of213.7-214.3℃。
Characterization data:1H NMR(400MHz,DMSO-d6)δ7.81-7.73(m,2H),7.53(dd,J＝8.5,5.7Hz,2H),7.32(t,J＝8.8Hz,2H),6.98(t,J＝8.8Hz,2H),3.90(s,6H).13C NMR(101MHz,DMSO-d6)δ190.6,188.0,185.8,165.7(d,J＝253.0Hz),164.3(d,J＝249.2Hz),137.5(d,J＝2.9Hz),132.4(d,J＝9.6Hz),131.8(d,J＝9.1Hz),130.5(d,J＝2.7Hz),116.2(d,J＝22.2Hz),115.1(d,J＝21.9Hz),102.1,41.9.19F NMR(376MHz,DMSO-d6)δ-104.51,-108.62.HRMS m/z(ESI)calcd for C18H14F2O4S(M+Na)+387.0473,found 387.0473
example 4
This example prepares α, α, β -tricarbonylthioylide compounds having the following structural formula:
the preparation method comprises the following steps: to a 25ml schlenk tube equipped with a magnetic stirrer was added 4-bromophenyl thioylide (0.4mmol, 109.6mg), Cu (OAc)2(0.04mmol，7.2mg)、CF3COOAg (0.04mmol, 8.8 mg). The reaction tube was replaced with oxygen three times under reduced pressure. After addition of 2ml of anhydrous 1, 4-dioxane, the reaction was stirred at 90 ℃ for 12 hours. After the reaction is finished, adding 200-mesh column chromatography silica gel, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the crude product, eluting with mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate: 1), carrying out TLC (thin layer chromatography) elution tracking detection, collecting eluent containing a target product, combining the target product eluent, and concentrating under reduced pressure to obtain the alpha, beta-tricarbonyl thioylide compound shown in the formula III-4 with the yield of 71%. The material is a white solid with a melting point of 215.8-217.4 ℃.
Characterization data:1H NMR(400MHz,DMSO-d6)δ7.73-7.69(m,2H),7.62(d,J＝8.5Hz,2H),7.42-7.35(m,4H),3.89(s,6H).13C NMR(101MHz,DMSO-d6)δ191.0,188.2,185.8,140.0,132.8,132.2,131.3,131.2,131.0,128.3,125.4,101.6,42.0.HRMS m/z(ESI)calcd for C18H14Br2O4S(M+Na)+506.8872,found 506.8871.
example 5
This example prepares α, α, β -tricarbonylthioylide compounds having the following structural formula:
the preparation method comprises the following steps: to a 25ml schlenk tube equipped with a magnetic stirrer was added 3-fluorophenylthionylylide (0.4mmol, 85.6mg), Cu (OAc)2(0.04mmol，7.2mg)、CF3COOAg (0.04mmol, 8.8 mg). The reaction tube was replaced with oxygen three times under reduced pressure. After addition of 2ml of anhydrous 1, 4-dioxane, the reaction was stirred at 90 ℃ for 12 hours. After the reaction is finished, adding 200-mesh column chromatography silica gel, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the crude product, eluting with mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate: 1), carrying out TLC (thin layer chromatography) elution tracking detection, collecting eluent containing a target product, combining the target product eluent, and concentrating under reduced pressure to obtain the alpha, beta-tricarbonyl thioylide compound shown in the formula III-5 with the yield of 65%. This material was a white solid with a melting point of 214.7-216.5 ℃.
Characterization data:1H NMR(400MHz,DMSO-d6)δ7.56(t,J＝5.2Hz,2H),7.50(m,1H),7.44(d,J＝9.4Hz,1H),7.31(s,1H),7.29(s,1H),7.24(q,J＝7.7Hz,1H),7.15(t,J＝8.0Hz,1H),3.92(s,6H).13C NMR(101MHz,DMSO-d6)δ190.3(d,J＝2.2Hz),187.8,185.4,162.4(d,J＝245.6Hz),161.8(d,J＝245.5Hz),143.1(d,J＝6.6Hz),135.9(d,J＝6.3Hz),131.4(d,J＝7.9Hz),130.6(d,J＝7.9Hz),125.8(d,J＝2.9Hz),125.0(d,J＝3.0Hz),121.2(d,J＝21.6Hz),118.4(d,J＝21.0Hz),116.0(d,J＝22.5Hz),115.4,102.4,41.9.19F NMR(376MHz,DMSO-d6)δ-112.14,-113.34.HRMS m/z(ESI)calcd for C18H14F2O4S(M+Na)+387.0473,found 387.0472.
example 6
This example prepares α, α, β -tricarbonylthioylide compounds having the following structural formula:
the preparation method comprises the following steps: to a 25ml schlenk tube equipped with a magnetic stirrer was added 2-fluorophenylthionylylide (0.4mmol, 85.6mg), Cu (OAc)2(0.04mmol，7.2mg)、CF3COOAg (0.04mmol, 8.8 mg). The reaction tube was replaced with oxygen three times under reduced pressure. After addition of 2ml of anhydrous 1, 4-dioxane, the reaction was stirred at 90 ℃ for 12 hours. After the reaction is finished, adding 200-mesh column chromatography silica gel, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the crude product, eluting with mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate: 1:2), carrying out TLC elution tracking detection, collecting eluent containing a target product, combining the target product eluent, and carrying out evaporation concentration to obtain the alpha, beta-tricarbonyl thioylide compound shown in the formula III-6 with the yield of 60%. This material was a yellow solid with a melting point of 164.6-166.8 ℃.
Characterization data:1H NMR(400MHz,DMSO-d6)δ7.81(m,1H),7.74-7.67(m,1H),7.42-7.28(m,4H),7.16-7.09(m,1H),7.06(t,J＝7.4Hz,1H),3.81(s,6H).13C NMR(101MHz,DMSO-d6)δ187.8,183.4,162.1(d,J＝256.2Hz),159.3(d,J＝247.4Hz),136.6(d,J＝9.2Hz),132.5(d,J＝8.5Hz),130.8(d,J＝1.8Hz),129.9(d,J＝3.3Hz),129.5(d,J＝15.8Hz),125.3(d,J＝3.3Hz),124.3(d,J＝3.4Hz),122.1(d,J＝10.6Hz),117.1,116.9,115.8,115.6,41.8.19F NMR(376MHz,DMSO-d6)δ-109.58,-115.44.HRMS m/z(ESI)calcd for C18H14F2O4S(M+Na)+387.0471,found387.0472.
example 7
This example prepares α, α, β -tricarbonylthioylide compounds having the following structural formula:
the preparation method comprises the following steps: to a 25ml schlenk tube equipped with a magnetic stirrer was added 3, 5-difluorophenylthioylide (0.4mmol, 92.8mg), Cu (OAc)2(0.04mmol，7.2mg)、CF3COOAg (0.04mmol, 8.8 mg). The reaction tube was replaced with oxygen three times under reduced pressure. After addition of 2ml of anhydrous 1, 4-dioxane, the reaction was stirred at 90 ℃ for 12 hours. After the reaction is finished, adding 200-mesh column chromatography silica gel, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the crude product, eluting with mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate: 1), carrying out TLC (thin layer chromatography) elution tracking detection, collecting eluent containing a target product, combining the target product eluent, and carrying out evaporation concentration to obtain the alpha, beta-tricarbonyl thioylide compound shown in the formula III-7 with the yield of 58%. This material was a white solid with a melting point of 236.5-237.6 ℃.
Characterization data:1H NMR(400MHz,DMSO-d6)δ7.63(s,1H),7.43(s,2H),7.25(s,3H),3.94(s,6H).13C NMR(101MHz,DMSO-d6)δ188.6,186.4,184.6,163.8(dd,J＝54.1,12.3Hz),161.3(dd,J＝53.3,12.3Hz),144.2(t,J＝8.3Hz),136.7(t,J＝8.1Hz),112.7-112.1(m,2C),109.8(t,J＝26.2Hz),106.7(t,J＝25.9Hz),102.3,41.9.19F NMR(376MHz,DMSO-d6)δ-107.96,-109.28.HRMS m/z(ESI)calcd for C18H12F4O4S(M+Na)+324.0284,found 324.0284.
example 8
This example prepares α, α, β -tricarbonylthioylide compounds having the following structural formula:
the preparation method comprises the following steps: to a 25ml schlenk tube equipped with a magnetic stirrer was added 4-methoxyphenyl thioylide (0.4mmol, 90.4mg), Cu (OAc)2(0.04mmol，7.2mg)、CF3COOAg(0.04mmol8.8 mg). The reaction tube was replaced with oxygen three times under reduced pressure. After addition of 2ml of anhydrous 1, 4-dioxane, the reaction was stirred at 90 ℃ for 12 hours. After the reaction is finished, adding 200-mesh column chromatography silica gel, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the crude product, eluting with mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate: 1:2), carrying out TLC (thin layer chromatography) elution tracking detection, collecting eluent containing a target product, combining the target product eluent, and concentrating under reduced pressure to obtain the alpha, beta-tricarbonyl sulfur ylide compound shown in the formula III-8 with the yield of 72%. This material was a white solid with a melting point of 191.6-192.7 ℃.
Characterization data:1H NMR(400MHz,DMSO-d6)δ7.61(d,J＝8.5Hz,2H),7.40(d,J＝8.4Hz,2H),6.97(d,J＝8.5Hz,2H),6.64(d,J＝8.4Hz,2H),3.86(s,6H),3.84(s,3H),3.66(s,3H).13C NMR(101MHz,DMSO-d6)δ191.0,188.3,186.2,163.8,162.3,133.5,131.8,131.5,127.0,114.2,113.3,102.2,56.1,55.7,41.9.HRMS m/z(ESI)calcd for C20H20O6S(M+H)+389.1053,found 389.1060.
example 9
This example prepares α, α, β -tricarbonylthioylide compounds having the following structural formula:
the preparation method comprises the following steps: to a 25ml schlenk tube equipped with a magnetic stirrer was added 4-cyanophenylthioylide (0.4mmol, 88.4mg), Cu (OAc)2(0.04mmol，7.2mg)、CF3COOAg (0.04mmol, 8.8 mg). The reaction tube was replaced with oxygen three times under reduced pressure. After addition of 2ml of anhydrous 1, 4-dioxane, the reaction was stirred at 90 ℃ for 12 hours. After the reaction is finished, column chromatography silica gel of 200 meshes is added, the solvent is removed by reduced pressure distillation, and the crude product is subjected to silica gel column layerSeparating, eluting with mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate: 1:2), tracking and detecting by TLC elution, collecting eluate containing target product, mixing the target product eluates, and concentrating under reduced pressure to obtain α, α, β -tricarbonyl thioylide compound shown by formula III-9 with a yield of 56%. This material was a yellow solid with a melting point of 232.2-233.9 ℃.
Characterization data:1H NMR(400MHz,DMSO-d6)δ7.99(d,J＝8.3Hz,2H),7.90(d,J＝8.1Hz,2H),7.72(d,J＝7.9Hz,2H),7.63(d,J＝8.0Hz,2H),3.90(s,6H).13C NMR(101MHz,DMSO-d6)δ190.5,187.7,183.2,144.9,136.9,133.2,132.3,129.9,129.3,118.7,118.6,116.1,113.5,102.7,42.0.HRMS m/z(ESI)calcd for C20H14N2O4S(M+H)+379.0747,found 379.0745.
example 10
This example prepares α, α, β -tricarbonylthioylide compounds having the following structural formula:
the preparation method comprises the following steps: to a 25ml schlenk tube equipped with a magnetic stirrer was added 4-nitrophenyl sulfide ylide (0.4mmol, 96.4mg), Cu (OAc)2(0.04mmol，7.2mg)、CF3COOAg (0.04mmol, 8.8 mg). The reaction tube was replaced with oxygen three times under reduced pressure. After addition of 2ml of anhydrous 1, 4-dioxane, the reaction was stirred at 90 ℃ for 12 hours. After the reaction is finished, adding 200-mesh column chromatography silica gel, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the crude product, eluting with mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate: 1), carrying out TLC (thin layer chromatography) elution tracking detection, collecting eluent containing a target product, combining the target product eluent, and concentrating under reduced pressure to obtain the alpha, beta-tricarbonyl thioylide compound shown in the formula III-10 with the yield of 61%. This material was a yellow solid with a melting point of 197.1-198.7 ℃.
Characterization data:1H NMR(400MHz,DMSO-d6)δ8.31(d,J＝8.4Hz,2H),8.10(d,J＝8.3Hz,2H),8.02(d,J＝8.3Hz,2H),7.72(d,J＝8.3Hz,2H),3.91(s,6H).13C NMR(101MHz,DMSO-d6)δ190.3,187.3,183.6,150.6,148.9,146.6,138.4,130.7,129.7,124.4,123.5,102.0,42.1.HRMS m/z(ESI)calcd for C18H14N2O8S(M+H)+419.0544,found419.0545.
example 11
This example prepares α, α, β -tricarbonylthioylide compounds having the following structural formula:
the preparation method comprises the following steps: to a 25ml schlenk tube equipped with a magnetic stirrer was added 2-naphthyloxysulfide ylide (0.4mmol, 98.4mg), Cu (OAc)2(0.04mmol，7.2mg)、CF3COOAg (0.04mmol, 8.8 mg). The reaction tube was replaced with oxygen three times under reduced pressure. After addition of 2ml of anhydrous 1, 4-dioxane, the reaction was stirred at 90 ℃ for 12 hours. After the reaction is finished, adding 200-mesh column chromatography silica gel, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the crude product, eluting with mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate: 1:2), carrying out TLC (thin layer chromatography) elution tracking detection, collecting eluent containing a target product, combining the target product eluent, and concentrating under reduced pressure to obtain the alpha, beta-tricarbonyl thioylide compound shown in the formula III-11 with the yield of 42%. This material was a white solid with a melting point of 239.8-241.2 ℃.
Characterization data:1H NMR(400MHz,DMSO-d6)δ8.25(s,1H),8.09(s,1H),8.01(d,J＝8.1Hz,1H),7.86(d,J＝8.1Hz,1H),7.73(t,J＝7.3Hz,3H),7.64(t,J＝7.0Hz,1H),7.58(t,J＝7.1Hz,1H),7.53-7.44(m,2H),7.38-7.26(m,2H),7.04(t,J＝6.9Hz,1H),4.01(s,6H).13C NMR(101MHz,DMSO-d6)δ191.8,189.4,186.2,138.3,135.5,134.3,132.2,131.5(2C),131.1,130.4,130.0,129.2,128.5,128.4,128.0,127.9,127.7,127.3,126.4,125.2,124.1,102.9,42.0.HRMS m/z(ESI)calcd for C26H20O4S(M+H)+429.1155,found429.1161.
example 12
This example prepares α, α, β -tricarbonylthioylide compounds having the following structural formula:
the preparation method comprises the following steps: to a 25ml schlenk tube equipped with a magnetic stirrer was added 2-furanthiofolide (0.4mmol, 74.4mg), Cu (OAc)2(0.04mmol，7.2mg)、CF3COOAg (0.04mmol, 8.8 mg). The reaction tube was replaced with oxygen three times under reduced pressure. After addition of 2ml of anhydrous 1, 4-dioxane, the reaction was stirred at 90 ℃ for 12 hours. After the reaction is finished, adding 200-mesh column chromatography silica gel, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the crude product, eluting with mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate: 1:4), carrying out TLC (thin layer chromatography) elution tracking detection, collecting eluent containing a target product, combining the target product eluent, and concentrating under reduced pressure to obtain the alpha, beta-tricarbonyl thioylide compound shown in the formula III-12 with the yield of 55%. This material was a yellow solid with a melting point of 184.9-187.2 ℃.
Characterization data:1H NMR(400MHz,DMSO-d6)δ8.02(d,J＝1.7Hz,1H),7.58(dd,J＝1.7,0.8Hz,1H),7.41-7.24(m,1H),6.96(dd,J＝3.6,0.8Hz,1H),6.73(dd,J＝3.6,1.7Hz,1H),6.46(dd,J＝3.5,1.7Hz,1H),3.86(s,6H).13C NMR(101MHz,DMSO-d6)δ183.6,180.0,175.2,152.9,150.2,149.0,146.5,121.3,117.5,113.1,112.5,100.0,41.9.HRMS m/z(ESI)calcd for C14H12O6S(M+H)+309.0427,found 309.0432.
example 13
This example prepares α, α, β -tricarbonylthioylide compounds having the following structural formula:
the preparation method comprises the following steps: to a 25ml schlenk tube equipped with a magnetic stirrer was added cyclohexylthioylide (0.4mmol, 80.8mg), Cu (OAc)2(0.04mmol，7.2mg)、CF3COOAg (0.04mmol, 8.8 mg). The reaction tube was replaced with oxygen three times under reduced pressure. After addition of 2ml of anhydrous 1, 4-dioxane, the reaction was stirred at 90 ℃ for 12 hours. After the reaction is finished, adding 200-mesh column chromatography silica gel, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the crude product, eluting with mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate: 2:1), carrying out TLC (thin layer chromatography) elution tracking detection, collecting eluent containing a target product, combining the target product eluent, and concentrating under reduced pressure to obtain the alpha, beta-tricarbonyl thioylide compound shown in the formula III-13 with the yield of 51%. This material was a yellow solid with a melting point of 129.8-133.4 ℃.
Characterization data:1H NMR(400MHz,DMSO-d6)δ3.63(s,6H),3.11(s,1H),1.91(d,J＝9.2Hz,2H),1.74-1.67(m,6H),1.62(d,J＝11.7Hz,2H),1.31-1.10(m,11H).13C NMR(101MHz,DMSO-d6)δ205.1,197.0,187.4,96.3,46.9,46.2,42.7,29.2,28.4,26.2,26.1,26.0,25.8.HRMS m/z(ESI)calcd for C18H18O4S(M+H)+341.1781,found 341.1784.
finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (5)
1. A synthetic method of an alpha, beta-tricarbonyl sulfur ylide compound is characterized in that the synthetic method is to take sulfur oxide ylide shown in a formula I as a raw material to react in an organic solvent under the action of a catalyst;
the α, α, β -tricarbonylthioylide compound has the structure of formula ii:
wherein R in the formula I is selected from substituted or unsubstituted alkyl, C6-10 aryl or C4-10 heterocycle, the substituent comprises alkyl, alkoxy, cyano, nitro and halogen, and the alkyl or alkoxy is substituted by 0, 1 or more halogen atoms;
the catalyst comprises: anhydrous copper acetate and/or silver trifluoroacetate; the reaction atmosphere is oxygen.
2. The method for synthesizing an α, α, β -tricarbonyl sulfide ylide compound as claimed in claim 1, wherein R comprises any one of the following groups:
3. the method of claim 1, wherein the organic solvent comprises 1, 4-dioxane.
4. The method for synthesizing the alpha, beta-tricarbonyl sulfur ylide compound as claimed in claim 1, wherein the reaction temperature is 70-110 ℃, and the reaction time is 8-14 h; after the reaction, the product is purified by silica gel column chromatography separation.
5. The method for synthesizing an α, α, β -tricarbonyl sulfide ylide compound as claimed in claim 1, wherein the ratio of the amount of the sulfur oxide ylide to the amount of the catalyst substance is 1 (0.1-0.2); the amount of the organic solvent added is 4-8 mL/mmol based on the amount of the sulfur oxide ylide substance represented by formula I.
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