CN110872249B - Synthetic method of alpha, beta-tricarbonyl sulfur ylide compound - Google Patents

Synthetic method of alpha, beta-tricarbonyl sulfur ylide compound Download PDF

Info

Publication number
CN110872249B
CN110872249B CN201911250278.3A CN201911250278A CN110872249B CN 110872249 B CN110872249 B CN 110872249B CN 201911250278 A CN201911250278 A CN 201911250278A CN 110872249 B CN110872249 B CN 110872249B
Authority
CN
China
Prior art keywords
tricarbonyl
reaction
ylide
beta
alpha
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911250278.3A
Other languages
Chinese (zh)
Other versions
CN110872249A (en
Inventor
邹亮华
施凯
闫成
朱帅
朱昊
成宇昊
徐佳伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangnan University
Original Assignee
Jiangnan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangnan University filed Critical Jiangnan University
Priority to CN201911250278.3A priority Critical patent/CN110872249B/en
Publication of CN110872249A publication Critical patent/CN110872249A/en
Application granted granted Critical
Publication of CN110872249B publication Critical patent/CN110872249B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

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

Synthetic method of alpha, beta-tricarbonyl sulfur ylide compound
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;
Figure BDA0002308823190000011
in one embodiment, the R comprises any one of the following groups:
Figure BDA0002308823190000012
Figure BDA0002308823190000021
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:
Figure BDA0002308823190000022
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:
Figure BDA0002308823190000023
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:
Figure BDA0002308823190000031
in some embodiments of the invention:
in example 1R is
Figure BDA0002308823190000032
In example 2R is
Figure BDA0002308823190000033
In example 3R is
Figure BDA0002308823190000034
In example 4R is
Figure BDA0002308823190000035
In example 5R is
Figure BDA0002308823190000036
In example 6R is
Figure BDA0002308823190000037
In example 7R is
Figure BDA0002308823190000041
In example 8R is
Figure BDA0002308823190000042
In example 9R is
Figure BDA0002308823190000043
In example 10R is
Figure BDA0002308823190000044
In example 11R is
Figure BDA0002308823190000045
In example 12R is
Figure BDA0002308823190000046
In example 13R is
Figure BDA0002308823190000047
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:
Figure BDA0002308823190000048
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:
Figure BDA0002308823190000051
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:
Figure BDA0002308823190000052
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:
Figure BDA0002308823190000061
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:
Figure BDA0002308823190000071
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:
Figure BDA0002308823190000072
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:
Figure BDA0002308823190000081
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:
Figure BDA0002308823190000091
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:
Figure BDA0002308823190000092
Figure BDA0002308823190000101
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:
Figure BDA0002308823190000102
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:
Figure BDA0002308823190000111
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:
Figure BDA0002308823190000112
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:
Figure BDA0002308823190000121
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;
Figure FDA0003179510440000011
the α, α, β -tricarbonylthioylide compound has the structure of formula ii:
Figure FDA0003179510440000012
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:
Figure FDA0003179510440000013
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.
CN201911250278.3A 2019-12-09 2019-12-09 Synthetic method of alpha, beta-tricarbonyl sulfur ylide compound Active CN110872249B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911250278.3A CN110872249B (en) 2019-12-09 2019-12-09 Synthetic method of alpha, beta-tricarbonyl sulfur ylide compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911250278.3A CN110872249B (en) 2019-12-09 2019-12-09 Synthetic method of alpha, beta-tricarbonyl sulfur ylide compound

Publications (2)

Publication Number Publication Date
CN110872249A CN110872249A (en) 2020-03-10
CN110872249B true CN110872249B (en) 2021-10-08

Family

ID=69717535

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911250278.3A Active CN110872249B (en) 2019-12-09 2019-12-09 Synthetic method of alpha, beta-tricarbonyl sulfur ylide compound

Country Status (1)

Country Link
CN (1) CN110872249B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114976247A (en) * 2022-06-17 2022-08-30 珠海冠宇动力电池有限公司 Electrolyte and battery containing same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109912503A (en) * 2019-04-01 2019-06-21 江南大学 A kind of synthetic method of 2,3- diacyl quinolines

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109912503A (en) * 2019-04-01 2019-06-21 江南大学 A kind of synthetic method of 2,3- diacyl quinolines

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
A New Synthesis of Phosphorane Ylide Precursors to Vicinal Tricarbonyls from Alkyl Halides Utilizing a Novel Phenylsulfonyl Reagent;Kieseung Lee 等;《Journal of the Korean Chemical Society》;20151231;第1-4页 *
Direct Access to 1,1-Dicarbonyl Sulfoxonium Ylides from Aryl Halides or Triflates: Palladium-Catalyzed Carbonylation;Yang Yuan 等;《Org. Lett.》;20190626;第5310-5314页 *
Formal [4 + 1] Annulation of α‑Arylhydrazonoketones and Dimethylsulfoxonium Methylide: One-pot Synthesis of Substituted Pyrazoles and Dihydropyrazoles;Qian Zhang 等;《J. Org. Chem.》;20160621;第6036-6041页 *
Manganese(I) and Rhenium(I) Tricarbonyl (Alkylthio)methyl and Alkylidenesulfonium Complexes;Eva Hevia 等;《Organometallics》;20021231;第5312-5319页 *
Reaction of oxosulfonium phenacylides with arylglyoxals. Effects of bis(acetylacetonato)copper(II);Takebayashi, Matsuji;《Kinki Daigaku Rikogakubu Kenkyu Hokoku》;19821231;第33-38页 *
Reactions of copper carbenoids with sulfoxides;Takebayashi, Matsuji 等;《Chemistry Letters》;19731231;第8卷;第809-812页 *

Also Published As

Publication number Publication date
CN110872249A (en) 2020-03-10

Similar Documents

Publication Publication Date Title
CN108299423B (en) Synthesis method of dihydropyrrolo-2-aminoquinoline compound
CN110872249B (en) Synthetic method of alpha, beta-tricarbonyl sulfur ylide compound
CN108314658B (en) A kind of preparation method of polysubstituted oxazole derivatives
CN110256444B (en) Method for synthesizing benzimidazoloquinazolinone compound
Liu et al. Synthesis of heteroarylidene malonate derived bis (thiazolines) and their application in the catalyzed Friedel–Crafts reaction
CN111253208A (en) Preparation method of 1-iodoalkyne
CN108610304B (en) Synthetic method of diaryl sultam compound
CN112500339B (en) Synthesis method of 8-acylquinoline derivative
CN113149924B (en) Simple preparation method of isoxazoline
CN113666883A (en) Method for synthesizing 4-vinyl isoxazole derivative
CN110627722B (en) Synthesis method of 7-alkynyl azepine derivative
CN107827705A (en) A kind of single arylation method of dichloro benzene-like compounds
CN111995554A (en) Method for preparing asymmetric organic selenium ether compound by metal-free chemical oxidation method
CN113717103B (en) Preparation method of ketone compound
Wang et al. Axial [6, 6′-(2, 4-pentadioxy)]-1, 1′-biphenyl-2, 2′-diamine (PD-BIPHAM): practical synthesis and applications in asymmetric hydrogenation
CN113004215B (en) Synthetic method of 2,4, 5-trisubstituted oxazole compound
CN110845310A (en) Method for iodinating ortho-position of benzaldehyde compound
CN110240554B (en) Alpha-thioether aryl acetonitrile compound and synthetic method thereof
CN106883229A (en) A kind of preparation method of 3 hydroxy imidazoles simultaneously [1,2 a] pyridine derivate
Klimczak et al. Reverse regioselectivity in Pd (0)/InI-mediated allylation of aldehydes with ε-amido-allylindiums generated from β-lactams. A new entry to non-racemic highly substituted γ-butyrolactones
CN110540522A (en) Synthesis method of N-nitro-N-allyl pyridine-2-amine compound
Ping et al. Carbene insertion into acyl CH bonds: Rh (III)-catalyzed cross-coupling of 2-aminobenzaldehydes with conjugated enynones
LU500625B1 (en) Synthetic Method of alpha, alpha, beta-tricarbonyl Sulfide Ylide Compound
CN115232163B (en) Silicon center chiral molecular compound and preparation method and application thereof
CN104193667A (en) Synthesis method of divergently oriented azacycles

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant