CN110872249A - Synthesis method of α -tricarbonyl sulfur ylide compound - Google Patents
Synthesis method of α -tricarbonyl sulfur ylide compound Download PDFInfo
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Abstract
The invention relates to a synthesis method of α -tricarbonyl sulfur ylide compound, which comprises the steps of taking sulfur oxide ylide shown in formula I as a raw material in an organic solvent, 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, 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 α -tricarbonyl sulfur ylide compound and a synthetic 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 above problems, the invention provides a synthesis method of α -tricarbonyl sulfur ylide compound, which is characterized in that the synthesis method comprises the step of taking sulfur oxide ylide shown in formula I as a raw material in an organic solvent, and reacting under the action of a catalyst, wherein R in formula I is selected from substituted or unsubstituted alkyl, C6-10 aryl or C4-10 heterocycle, a 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.
And the purification method comprises the steps of adding column chromatography silica gel after the reaction is finished, distilling under reduced pressure to remove the solvent, spin-drying until the silica gel adsorbs the product powder, loading the product powder onto a column, eluting and collecting by using a mixed solution of petroleum ether and ethyl acetate, and concentrating under reduced pressure to obtain the α -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 -tricarbonyl sulfide ylide compound prepared according to the above synthesis method, wherein the α -tricarbonyl sulfide ylide compound has a 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 synthesis method of α -tricarbonyl sulfur ylide compound, which has the advantages of cheap and easily synthesized raw materials, cheap and easily obtained catalyst, high efficiency, green color, wide substrate range, good electron withdrawing and electron donating group tolerance, synthesis of sulfur ylide of heterocyclic substituent and alkane substituent, highest yield up to 82 percent and simple operation.
And provides α -tricarbonyl sulfur ylide compound which can be further reacted to generate tetraone compound, such as DPBT, and the compound usually needs mercury, nitric acid and other toxic and harmful substances in synthesis.
Drawings
FIG. 1 is a single crystal structural diagram of α -tricarbonyl sulfide ylide 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 prepared α -tricarbonylthioylide compounds having the formula:
the preparation method comprises the following steps: to a magnetic stirrerA25 ml schlenk tube was charged with thioylide oxide (0.4mmol, 78.4mg), Cu (OAc)2(0.04mmol，7.2mg)、CF3COOAg (0.04mmol, 8.8mg), under reduced pressure, the reaction tube was purged with oxygen three times, 2ml of anhydrous 1, 4-dioxane was added, the reaction was stirred at 90 ℃ for 12 hours, after the reaction was completed, 200 mesh column chromatography silica gel was added, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, and eluted with a mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate ═ 1:2), followed by TLC elution, an eluate containing the target product was collected, the target product eluates were combined, and concentrated under reduced pressure to obtain α -tricarbonylthioylide compound represented by formula iii-1, the yield was 81%, the substance was a white solid, the melting point was 234.6 to 235.8 ℃, and the single crystal structure of α -tricarbonylthioylide compound was tested by an X-ray diffraction tester to obtain a structural analysis chart shown in fig. 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 prepared α -tricarbonylthioylide compounds having the 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, 200 meshes of column chromatography silica gel is added, the solvent is removed by reduced pressure distillation, the crude product is separated by the column chromatography of the silica gel, and petroleum ether and ethyl acetate (stone) are addedEluting with a mixed solution of oil ether and ethyl acetate 1:1), tracking and detecting by TLC (thin layer chromatography), collecting eluent containing a target product, combining the target product eluent, and concentrating under reduced pressure to obtain α -tricarbonyl sulfur ylide compound shown as formula III-2 with the yield of 81%.
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).13CNMR(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 prepared α -tricarbonylthioylide compounds having the 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, 8.8mg), under reduced pressure, the reaction tube was purged with oxygen three times, 2ml of anhydrous 1, 4-dioxane was added, the reaction was stirred at 90 ℃ for 12 hours, after the reaction was completed, 200 mesh column chromatography silica gel was added, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, and eluted with a mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate ═ 1:2), followed by TLC elution, an eluate containing the target product was collected, the target product eluates were combined, and concentrated under reduced pressure to obtain α -tricarbonylthioylide compound represented by formula iii-3 in 73% yield, which was a white solid having a melting point of 213.7-214.3 ℃.
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 prepared α -tricarbonylthioylide compounds having the 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, 8.8mg), under reduced pressure, the reaction tube was purged with oxygen three times, 2ml of anhydrous 1, 4-dioxane was added, the reaction was stirred at 90 ℃ for 12 hours, after the reaction was completed, 200 mesh column chromatography silica gel was added, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, and eluted with a mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate 1:1), followed by TLC elution detection, the eluates containing the target product were collected, the target product eluates were combined, and concentrated under reduced pressure to obtain α -tricarbonylthioylide compound represented by formula iii-4, with a yield of 71%, which was a white solid having a melting point of 215.8 to 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 forC18H14Br2O4S(M+Na)+506.8872,found 506.8871.
example 5
This example prepared α -tricarbonylthioylide compounds having the 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, 8.8mg), under reduced pressure, the reaction tube was purged with oxygen three times, 2ml of anhydrous 1, 4-dioxane was added, the reaction was stirred at 90 ℃ for 12 hours, after the reaction was completed, 200 mesh column chromatography silica gel was added, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, and eluted with a mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate 1:1), followed by TLC elution detection, the eluate containing the target product was collected, the target product eluates were combined, and concentrated under reduced pressure to obtain α -tricarbonylthioylide compound represented by formula iii-5, yield 65% which was a white solid, melting point 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,found387.0472.
example 6
This example prepared α -tricarbonylthioylide compounds having the 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, 8.8mg), under reduced pressure, the reaction tube was purged with oxygen three times, 2ml of anhydrous 1, 4-dioxane was added, the reaction was stirred at 90 ℃ for 12 hours, after the reaction was completed, 200 mesh column chromatography silica gel was added, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, and eluted with a mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate ═ 1:2), followed by TLC elution, an eluate containing the target product was collected, the target product eluates were combined, and evaporated and concentrated to obtain α -tricarbonylthioylide compound represented by formula iii-6, with a yield of 60%, which was a yellow solid, a melting point of 164.6 to 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),117.1,116.9,115.8,115.6,41.8.19FNMR(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 prepared α -tricarbonylthioylide compounds having the formula:
the preparation method comprises the following steps: to a 25ml schlenk tube equipped with a magnetic stirrer were added 3, 5-difluorophenylthioylide (0.4mmol, 92.8mg), Cu (ROAc)2(0.04mmol，7.2mg)、CF3COOAg (0.04mmol, 8.8mg), under reduced pressure, the reaction tube was purged with oxygen three times, 2ml of anhydrous 1, 4-dioxane was added, the reaction was stirred at 90 ℃ for 12 hours, after the reaction was completed, 200 mesh column chromatography silica gel was added, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, and eluted with a mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate 1:1), followed by TLC elution detection, the eluates containing the target product were collected, the target product eluates were combined, and evaporated and concentrated to obtain α -tricarbonylthioylide compound represented by formula iii-7, which was a white solid with a melting point of 236.5-237.6 ℃ in a yield of 58%.
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,found324.0284.
example 8
This example prepared α -tricarbonylthioylide compounds having the 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 (0.04mmol, 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 meshes of column chromatography silica gel, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the crude product, and adding petroleum ether and ethyl acetate (petroleum ether)Ethyl acetate 1:2), followed by TLC elution, collecting the target product-containing eluates, combining the target product eluates, and concentrating under reduced pressure to obtain α -tricarbonylthioylide compound represented by formula iii-8 in 72% yield, which is 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 prepared α -tricarbonylthioylide compounds having the 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, 8.8mg), under reduced pressure, displacing oxygen in the reaction tube three times, adding 2ml of anhydrous 1, 4-dioxane, stirring the reaction 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, separating the crude product by silica gel column chromatography, eluting with a mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate ═ 1:2), performing TLC elution tracking detection, collecting the eluent containing the target product, combining the eluates of the target product, and concentrating under reduced pressure to obtain α -tricarbonylthioylide compound represented by formula III-9, wherein the yield is 56%, the substance is yellow solid, and the melting point is 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,found379.0745.
example 10
This example prepared α -tricarbonylthioylide compounds having the 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, 8.8mg), under reduced pressure, the reaction tube was purged with oxygen three times, 2ml of anhydrous 1, 4-dioxane was added, the reaction was stirred at 90 ℃ for 12 hours, after the reaction was completed, 200 mesh column chromatography silica gel was added, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, and eluted with a mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate ═ 1:1), followed by TLC elution, an eluate containing the target product was collected, the target product eluates were combined, and concentrated under reduced pressure to obtain α -tricarbonylthioylide compound represented by formula iii-10, in a yield of 61%, which was a yellow solid, having 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 prepared α -tricarbonylthioylide compounds having the 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, 8.8mg), under reduced pressure, the reaction tube was purged with oxygen three times, 2ml of anhydrous 1, 4-dioxane was added, the reaction was stirred at 90 ℃ for 12 hours, after the reaction was completed, 200 mesh column chromatography silica gel was added, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, and eluted with a mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate ═ 1:2), followed by TLC elution, an eluate containing the target product was collected, the target product eluates were combined, and concentrated under reduced pressure to obtain α -tricarbonylthioylide compound represented by formula iii-11 in 42% yield, which was a white solid having 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).13CNMR(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 prepared α -tricarbonylthioylide compounds having the 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, 8.8mg), under reduced pressure, the reaction tube was purged with oxygen three times, 2ml of anhydrous 1, 4-dioxane was added, the reaction was stirred at 90 ℃ for 12 hours, after the reaction was completed, 200 mesh column chromatography silica gel was added, the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography, and eluted with a mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate ═ 1:4), followed by TLC elution, an eluate containing the target product was collected, the target product eluates were combined, and concentrated under reduced pressure to obtain α -tricarbonylthioylide compound represented by formula iii-12, in 55% yield, which was a yellow solid having a melting point of 184.9 to 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)calcdfor C14H12O6S(M+H)+309.0427,found 309.0432.
example 13
This example prepared α -tricarbonylthioylide compounds having the 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, and roughingSeparating the product by silica gel column chromatography, eluting with mixed solution of petroleum ether and ethyl acetate (petroleum ether: ethyl acetate: 2:1), tracking and detecting by TLC, collecting eluate containing target product, mixing the eluates, and concentrating under reduced pressure to obtain α -tricarbonyl sulfur ylide compound shown in formula III-13 with yield of 51%.
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.HRMSm/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 (7)
1. The synthesis method of the α -tricarbonyl sulfur ylide compound is characterized by comprising the following 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, a substituent comprises alkyl, alkoxy, cyano, nitro and halogen, and the alkyl or alkoxy is substituted by 0, 1 or more halogen atoms;
2. the method for synthesizing α -tricarbonyl sulfur ylide compound as claimed in claim 1, wherein R comprises any one of the following groups:
3. the synthesis method of α -tricarbonyl sulfur ylide compound as claimed in claim 1, wherein the catalyst comprises anhydrous cupric acetate and/or silver trifluoroacetate, and the organic solvent comprises 1, 4-dioxane.
4. The synthesis method of α -tricarbonyl sulfur ylide compound as claimed in claim 1, wherein the reaction temperature is 70-110 ℃, the reaction time is 8-14 h, the reaction atmosphere is oxygen, and the product is purified by silica gel column chromatography separation after the reaction.
5. The method for synthesizing α -tricarbonyl sulfur ylide compound according to claim 1, wherein the ratio of the sulfur oxide ylide to the amount of the catalyst substance is 1 (0.1-0.2), and the amount of the organic solvent is 4-8 mL/mmol based on the amount of the sulfur oxide ylide represented by formula I.
6. The α -tricarbonyl sulfur ylide compound prepared by the synthesis method of claims 1-5, wherein the α -tricarbonyl sulfur ylide compound has a 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.
7. The α -tricarbonyl sulfide ylide compound as claimed in claim 6, wherein R comprises the following group:
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