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Synthesis method of tetrahydro-oxanthone

A synthesis method and technology of xanthone are applied in the field of synthesis of tetrahydroxanthone, can solve problems such as easy isomerization, and achieve the effects of shortening synthesis route, reliable method and wide applicability of substrates

Pending Publication Date: 2022-05-27
SHAANXI UNIV OF SCI & TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Traditional synthetic methods such as Fries rearrangement and transition metal-catalyzed intramolecular tandem reactions can construct some simple tetrahydroxanthone skeletons (a) Roberts, J.C.Chem.Rev.1961, 61, 591-605. (b) Oldenberg , T.B.P.; Wilkes, H.; Horsfield, B.; van Duin, A.C.T.; Stoddart, D.; Willhelms, A.Org. Geochem. Chem. 2005, 12, 2413-2446. (d) El-Seedi, H.R.; El-Ghorab, D.M.H.; El-Barbary, M.A.; Zayed, M.F.; Goransson, U.; .Med.Chem.2009,16,2581-2626. But these methods usually have some disadvantages in terms of substrate pre-functionalization, stoichiometry of metal species and harsh reaction conditions
In recent years, the strategy of oxa-Michael addition and Dieckmann condensation has proven to be the most attractive strategy for the synthesis of tetrahydroxanthone skeletons in the field of total synthesis, because this method can be easily obtained from the starting materials and Mild reaction conditions form a tetrahydroxanthone three-membered ring skeleton: Lesch, B.; S.Angew.Chem.Int.Ed.2004,43,115-118. However, this type of method requires multi-step reactions, and isomerization is easily caused during the reaction

Method used

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  • Synthesis method of tetrahydro-oxanthone
  • Synthesis method of tetrahydro-oxanthone
  • Synthesis method of tetrahydro-oxanthone

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Experimental program
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Effect test

Embodiment 1

[0045] Preparation of 6-chloro-3,4-dihydro-1H-xanthene-1,9(2H)-dione

[0046]Dissolve 0.15 mmol of iodine ylide and 0.1 mmol of 4-chloro-2-hydroxybenzaldehyde in a reactor filled with 1 mL of HFIP, add 0.025 mmol of [Ru(p-cymene)Cl 2 ] 2 It was a catalyst, 0.2 mmol LiOAc was a base, stirred at 80 ° C for 12 h, monitored the progress of the reaction by TLC, and separated by column chromatography to obtain 16.6 mg of a pale yellow solid with a yield of 67%. The structural formula of the obtained product is as follows:

[0047]

[0048] like figure 1 and figure 2 As shown, the NMR characterization of the product: 1 HNMR (400MHz, CDCl 3 )δ7.98(d,J=8.2Hz 1H),7.51(s,1H),7.35(d,J=8.2Hz,1H),3.07(t,J=5.98Hz,2H),2.64(t,J =6.1Hz,2H),2.32(t,J=6.1Hz,2H); 13 CNMR (100MHz, CDCl 3 )194.5,171.3,154.5,130.8,125.1,122.4,122.2,116.3,111.8,37.7,23.8,22.4.

Embodiment 2

[0050] Preparation of 7-methoxy-3,4-dihydro-1H-xanthene-1,9(2H)-dione

[0051] Dissolve 0.15 mmol of iodine ylide and 0.1 mmol of 5-methoxy-2-hydroxybenzaldehyde in a reactor filled with 1 mL of HFIP, add 0.025 mmol of [Ru(p-cymene)Cl 2 ] 2 As the catalyst, 0.2 mmol NaOAc was used as the base, stirred at 80 ° C for 12 h, monitored the progress of the reaction by TLC, and separated by column chromatography to obtain 15.4 mg of white solid with a yield of 62.9%. The structural formula of the obtained product is as follows:

[0052]

[0053] like image 3 and Figure 4 As shown, the NMR characterization of the product: 1 HNMR (400MHz, CDCl 3 )δ7.57(d,J=2.4,1H),7.39(d,J=9.0Hz,1H),6.93(dd,J 1 =J 2 =9.0Hz,1H),3.91(s,3H),3.06(t,J=6.3Hz,2H),2.64(t,J=6.5Hz,2H),2.33-2.28(m,2H); 13 CNMR (100MHz, CDCl 3 )195.0,171.4,157.2,149.3,124.3,116.7,113.9,111.6,103.8,56.0,37.8,23.9,22.5.

Embodiment 3

[0055] Preparation of 7-fluoro-3,4-dihydro-1H-xanthene-1,9(2H)-dione

[0056] Dissolve 0.15 mmol of iodine ylide and 0.1 mmol of 5-fluoro-2-hydroxybenzaldehyde in a reactor filled with 1 mL of HFIP, add 0.025 mmol [Ru(p-cymene)Cl 2 ] 2 as catalyst, 0.2mmolKH 2 PO 4 As a base, stirred at 80 ° C for 12 h, monitored the progress of the reaction by TLC, and separated by column chromatography to obtain 14 mg of white solid with a yield of 60.3%. The structural formula of the obtained product is as follows:

[0057]

[0058] like Figure 5 and Image 6 As shown, the NMR characterization of the product: 1 HNMR (400MHz, CDCl 3 )δ7.76(dd,J 1 =J 2 =9.0Hz,1H),7.43(dd,J 1 =J 2 =9.0Hz,1H),7.08-7.03(m,1H),3.08(t,J=6.3Hz,2H),2.65(t,J=6.5Hz,2H),2.35-2.29(m,2H); 13 CNMR (100MHz, CDCl 3 )194.4,172.3,161.4,159.0,150.7,124.7,124.6,116.7,116.6,112.4,112.6,111.8,111.7,107.9,107.6,37.7,23.9,22.4.

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Abstract

The invention discloses a synthesis method of a tetrahydro-oxanthone compound, which comprises the following steps: adding iodine ylide, salicylaldehyde, a catalyst and alkali into a solvent, and after the reaction is completed, separating and purifying to obtain the tetrahydro-oxanthone compound. The synthesis method is simple and efficient, iodine ylide and salicylaldehyde which are stable and easy to obtain in air are used as reaction raw materials, in the presence of a solvent, a catalyst and alkali are added, and tetraoxyanthrone is efficiently synthesized under mild reaction conditions.

Description

technical field [0001] The invention belongs to the field of organic synthesis, in particular to a method for synthesizing tetrahydroxanthone. Background technique [0002] Tetrahydroxanthone compounds are widely used in the field of biomedicine. For example, they can be used in the development of new drugs according to their antibacterial activity, and also have important application value in the field of anti-cancer cells and malaria. Therefore, it is of great significance to study the efficient synthesis methods of such compounds. Conventional synthetic methods such as Fries rearrangement and transition metal-catalyzed intramolecular tandem reaction strategies enable the construction of some simple tetrahydroxanthone skeletons (a) Roberts, J.C.Chem.Rev.1961,61,591-605.(b)Oldenberg , T.B.P.; Wilkes, H.; Horsfield, B.; van Duin, A.C.T.; Stoddart, D.; Willhelms, A.Org. Chem. 2005, 12, 2413-2446. (d) El-Seedi, H.R.; El-Ghorab, D.M.H.; El-Barbary, M.A.; Zayed, M.F.; Goransso...

Claims

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Application Information

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IPC IPC(8): C07D311/86C07D311/78
CPCC07D311/86C07D311/78Y02P20/584
Inventor 李翔申阳
Owner SHAANXI UNIV OF SCI & TECH