A method for synthesizing paeoniflorin derivatives

Abstract

The present invention belongs to the field of organic chemical synthesis, and in particular to a method for synthesizing paeoniflorin derivatives. The specific technical scheme is: a method for preparing paeoniflorin derivatives, using Lewis acid as a catalyst, alcohols as a reaction solvent, paeoniflorin as a raw material, and alkylating the C-4 and C-9 positions of paeoniflorin through dehydration reaction and acetal reaction to prepare paeoniflorin derivatives. The synthetic method of the present invention has wider substrate adaptability and better product configuration stability, and the synthetic method has short steps, short reaction time, high yield, and simple synthetic operation. At the same time, the catalyst of the present invention has high catalytic activity and can be recycled, and has good application prospects in the fields of organic synthesis and drug development.

Description

Technical Field

[0001] The invention belongs to the field of organic chemical synthesis, and particularly relates to a method for synthesizing a paeoniflorin derivative. Background Art

[0002] Paeoniflorin and its derivatives can be used to treat autoimmune diseases such as systemic lupus erythematosus, Sjögren's syndrome, rheumatoid arthritis, etc., and also show excellent pharmacological activity in neurodegenerative diseases and metabolic diseases. Therefore, the organic synthesis of paeoniflorin and its derivatives is one of the important topics in the field of organic chemical synthesis.

[0003] At present, there has been no research on modifying the C-4 hydroxyl group of paeoniflorin to synthesize new structural derivatives, and existing research has focused on synthesizing known alkylated extracts.

[0004] Therefore, providing a more universal synthesis method to expand the synthesis of more alkylated paeoniflorin derivatives has important practical significance and application value. Summary of the invention

[0005] The purpose of the present invention is to provide a method for synthesizing paeoniflorin derivatives.

[0006] To achieve the above-mentioned purpose of the invention, the technical scheme adopted by the present invention is: a method for preparing paeoniflorin derivatives, using Lewis acid as a catalyst, alcohols as a reaction solvent, and paeoniflorin as a raw material, alkylating the C-4 and C-9 positions of paeoniflorin through dehydration reaction and acetal reaction to prepare paeoniflorin derivatives.

[0007] Preferably, the reaction equation is:

[0008]

[0009] R is one of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, benzyl and phenethyl.

[0010] Preferably, the alcohol is any one of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, benzyl alcohol, and phenylethyl alcohol, or a mixture of several of them.

[0011] Preferably, the molar ratio of paeoniflorin to Lewis acid is 1:1.

[0012] Preferably, the reaction temperature is the boiling point of the reaction solvent.

[0013] Preferably, when the obtained paeoniflorin derivative is a mixture of multiple paeoniflorin derivatives, the method for separating the paeoniflorin derivative mixture is: subjecting the mixture to acetylation of the hydroxyl groups on the glucose group, separating the obtained acetylated products from each other, and then subjecting each separated acetylated product to deacetylation.

[0014] Preferably, the conditions for the acetylation reaction of the hydroxyl group on the glucose group are: carrying out the reaction in a mixed solvent of pyridine:acetic anhydride in a volume ratio of 1:1, and reacting at 0° C. for 1 hour.

[0015] Preferably, the deacetylation reaction conditions are: adding triethylamine to the methanol solution for reaction, and reacting at room temperature for 24 hours.

[0016] Correspondingly, a paeoniflorin derivative prepared by the method for preparing a paeoniflorin derivative has a structural formula of:

[0017]

[0018] Correspondingly, a paeoniflorin derivative prepared by the method for preparing a paeoniflorin derivative has a structural formula of:

[0019]

[0020] The present invention has the following beneficial effects: the synthesis method of the present invention has wider substrate adaptability and better product configuration stability, and the synthesis method has short steps, short reaction time, high yield, and simple synthesis operation. At the same time, the catalyst of the present invention has high catalytic activity and can be recycled, and has good application prospects in the fields of organic synthesis and drug research and development. DETAILED DESCRIPTION

[0021] The present invention provides a method for synthesizing paeoniflorin derivatives in a simple and efficient manner under Lewis acid catalysis, comprising the following steps:

[0022] Under the catalysis of Lewis acid -Sc(CF3SO3)3, with alcohol solvent as reaction solvent and paeoniflorin as raw material, alkylation is performed on C-4 and C-9 of paeoniflorin through dehydration reaction and acetal reaction at the boiling point of the solvent (65-118°C), thereby preparing paeoniflorin derivatives. Specifically: paeoniflorin and Sc(CF3SO3)3 are heated to reflux in an alcohol solvent for reaction, and after the reaction is complete, the reaction solution is cooled to room temperature, the reaction solution is extracted, the solvent is evaporated under reduced pressure, and column chromatography is performed for separation to obtain paeoniflorin derivatives.

[0023] A preferred solution is that the alcohol solvent is any one of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, benzyl alcohol, and phenylethyl alcohol, or a mixture of several of them.

[0024] The products obtained are isomers with similar polarity. The obtained product mixture is subjected to hydroxyl acetylation reaction on the glucose group to produce a polarity difference between the products, thereby achieving the separation of the acetylated products. In order to obtain the target compound, the separated acetylated product is then subjected to a deacetylation reaction. In one embodiment: the glucose hydroxyl acetylation condition is to react the product mixture at 0°C in a solvent of pyridine: acetic anhydride = 1:1 (volume ratio) for 1h. The deacetylation condition is: react the acetylated product with triethylamine in a methanol solvent, the molar ratio of the acetylated product to triethylamine is 1:25, and react at room temperature for 24h.

[0025] The reaction equation is as follows.

[0026]

[0027] R is one of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, benzyl and phenethyl.

[0028] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art.

[0029] Embodiment 1

[0030] Paeoniflorin (240 mg, 0.5 mmol) was dissolved in CH3OH (12 mL), Sc(CF3SO3)3 (246 mg, 0.5 mmol) was added, and the mixture was refluxed at 65°C for 30 min. The reaction solution was poured into water, extracted 3 times with EtOAc (ethyl acetate), and then washed 3 times with saturated NaCl. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated to dryness. After the organic phase was concentrated, a mixture of compound 3 and compound 4 (224 mg, 90.7%) was obtained. Then, the mixture was added to Ac2O / Py (1:1, volume ratio, 6 mL) and reacted at 0°C for 1 h for hydroxyacetylation. After diluting the reaction solution with EtOAc, it was washed with 5% H2SO4 solution, and then washed with water and saturated NaHCO3 respectively. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated to dryness. Compounds 1 and 2 were separated and purified by column chromatography.

[0031] Compound 1, white powder, 127.2 mg, yield 42.4%. Its structural formula and test data are as follows:

[0032]

[0033] R f0.38 (petroleum:EtOAc, 1:1). 1 H NMR (400MHz, Chloroform-d) δ8.03 (d,J=6.9Hz 2H,H-2",H-6"),7.60(t,J=7.5Hz,1H,H-4"),7.47(t,J =7.7Hz,2H,H-3",H-5"),5.46(s,1H,H-9),5.13-4.96(m,3H,H-2',H-3',H-4'),4.75(d,J=7.8Hz,1H,H-1'),4.59(d,J=12.0Hz,1H,H-8),4.47 (d,J=12.0Hz,1H,H-8),4.18(dd,J=12.2,2.5Hz,1H,H-6'),4.11(dd, J=12.2,5.4Hz,1H,H-6'),3.64-3.58(m,1H,H-5'),3.41(s,3H,H-11),2.77(d,J=6.9Hz,1H,H-5),2.32(dd ,J=10.7,6.9Hz,1H,H-6),2.10-1.93(m,14H,4COCH3,H-3),1.79(d,J=10.6Hz,1H,H-6),1.36(s,3H,H-10). MS-ESI m / z Calcd for C 32 H 38 O 15 Na[M+Na] + :685.22,found 685.26.

[0034] Compound 2, white powder, 86.4 mg, yield 28.8%. Its structural formula and test data are as follows:

[0035]

[0036] R f 0.30 (petroleum: EtOAc, 1:1). 1H NMR(400MHz,Chloroform-d)δ8.01 (d,J=7.0Hz,2H,H-2",H-6"),7.63-7.57(m,1H,H-4"),7.46(t,J=7.7 Hz,2H,H-3",H-5"),5.16(t,J=9.4Hz,1H,H-3'),5.08-5.02(m,2H,H-2',H-4'),5.01(s,1H,H-9),4.78(d,J=7.9Hz,1H,H-1'),4.51(d,J=1.6 Hz,2H,H-8),4.19(dd,J=12.2,2.6Hz,1H,H-6'),4.14(d,J=5.5Hz,1H,H-6'),3.68-3.62(m,1H,H-5'),3.35(s,3H,H-11),3.04(d,J=7 .3Hz,1H,H-5),2.71(t,J=9.3Hz,1H,H-6),2.65(d,J=6.0Hz,2H,H-6,H-3),2.09-1.96(m,13H,4COCH3,H-3),1.40(s,3H,H-10).MS-ESI m / z Calcd for C 32 H 38 O 15 Na[M+Na] + :685.22,found 685.13.

[0037] Embodiment 2

[0038] Compound 1 (67 mg, 0.10 mmol) was dissolved in anhydrous CH3OH (3 mL), and Et3N (0.35 mL, 2.5 mmol) was added. After reacting at room temperature for 24 hours, the reaction solution changed from turbid to clear. The reaction solution was then poured into water, extracted 3 times with CH2Cl2, and washed 3 times with saturated NaCl. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated. Compound 3 was obtained by column chromatography purification. Compound 3 is a white powder, 22.3 mg, and a yield of 44.5%. Its structural formula and test data are as follows:

[0039]

[0040] R f 0.36 (CH2Cl2:CH3OH, 7:1). 1H NMR (400MHz, Chloroform-d) δ7.93 (d, J=7.2Hz, 2H, H-2", H-6"), 7.49 (t, J=7.4Hz, 1H, H-4"), 7.35 (t, J= 7.7Hz,2H,H-3",H-5"),5.49(s,1H,H-9),4.70-4.61(m,2H,H-8,H-1'), 4.50(d,J=7.7Hz,1H,H-1'),3.80(s,2H,H-6'),3.59(s,2H,H-3',H-4') ,3.42(s,1H,H-2'),3.34(s,4H,H-5',H-11),2.68(d,J=6.6Hz,1H,H-6), 2.39(d,J=10.0Hz,1H,H-5),1.95(s,2H,H-3),1.78(d,J=10.7Hz,1H,H-6),1.34(s,3H,H-10).MS-ESI m / z Calcd for C 24 H 30 O 11 Na[M+Na] + 517.49, found 517.20.

[0041] Embodiment 3

[0042] Compound 2 (83 mg, 0.13 mmol) was dissolved in anhydrous CH3OH (3 mL), and Et3N (0.45 mL, 3.25 mmol) was added. After reacting at room temperature for 24 hours, the reaction solution changed from turbid to clear. The reaction solution was then poured into water, extracted with CH2Cl2 three times, and washed with saturated NaCl three times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated. Compounds 4 and 5 were obtained by column chromatography.

[0043] Compound 4, white powder, 29.7 mg, yield 48%. Its structural formula and test data are as follows:

[0044]

[0045] R f 0.35 (CH2Cl2:CH3OH, 7:1). 1H NMR (400MHz, Chloroform-d) δ7.90 (d, J=7.7Hz, 2H, H-2", H-6"), 7.51 (t, J=7.4Hz, 1H, H-4"), 7.35 (t, J= 7.7Hz,2H,H-3",H-5"),5.02(s,1H,H-9),4.73(d,J=11.7Hz,1H,H-8),4.56(d,J=12.8Hz,2H,H-8,H-1'),3.84(s,2H,H-6'),3.64(s,2H,H-3', H-4'),3.48(s,1H,H-2'),3.35(s,1H,H-5'),3.27(s,3H,H-11),2.96(d, J=7.0Hz,1H,H-6),2.80(d,J=10.6Hz,1H,H-5),2.60(q,J=18.3Hz,2H,H-3),2.00(d,J=10.9Hz,1H,H-6),1.40(s,3H,H-10).MS-ESI m / z Calcd for C 24 H 30 O 11 Na[M+Na] + 517.49, found 518.16.

[0046] Compound 5, white powder, 15.4 mg, yield 31.5%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0047]

[0048] R f 0.08 (CH2Cl2:CH3OH, 7:1). 11H NMR (400 MHz, Acetone-d6) δ 5.10 (s, 1H, H-9), 4.76 (d, J = 7.7 Hz, 1H, H-8), 4.02 (d, J = 12.6 Hz, 1H, H-6'), 3.81 (dd, J = 11.7, 2.6 Hz, 1H, H-6'), 3.72 (d, J = 12.5 Hz, 1H, H-2'), 3.62 (dd, J = 10.2, 4.2 Hz, 2H, H-4', H-5'), 3.48 (t, J = 8.6 Hz, 1H, H-3'), 3.39 - 3.31 (m, 2H, H-8, H-1'), 3.26 (s, 3H, H-11), 2.90 (dd, J = 11.1, 7.3 Hz, 1H, H-5), 2.75 (d, J = 17.9 Hz, 1H, H-6), 2.48 (d, J = 7.5 Hz, 1H, H-3), 2.36 (d, J = 17.3 Hz, 1H, H-3), 2.07 (d, J = 4.2 Hz, 1H, H-6), 1.35 (s, 3H, H-10). 13 13C NMR (101 MHz, Acetone-d6) δ 205.27 (C-4), 105.31 (C-9), 98.93 (C-1'), 88.26 (C-1), 87.13 (C-2), 78.22 (C-3'), 77.54 (C-5'), 74.59 (C-2'), 71.77 (C-11), 65.21 (C-7), 62.97 (C-6'), 60.19 (C-8), 55.48 (C-4'), 47.17 (C-3), 46.66 (C-5), 26.67 (C-6), 20.75 (C-10). MS-ESI-TOF m / z Calcd for C 17 H 26 O 10 Na [M+Na] + 413.39, found 413.20.

[0049] Example 4

[0050] Paeoniflorin (240 mg, 0.5 mmol) was dissolved in EtOH (12 mL), catalyzed by Sc(CF3SO3)3 (246 mg, 0.5 mmol), and refluxed at 78°C for 45 min. The reaction solution was poured into water, extracted with EtOAc 3 times, and washed with saturated NaCl 3 times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated to dryness. After the organic phase was concentrated, a mixture of compounds 8 and 10 (219 mg, 86.2%) was obtained. Then, the mixture was added to Ac2O / Py (1:1, 6 mL) and reacted at 0°C for 1 h for hydroxyacetylation. After the reaction solution was diluted with EtOAc, it was washed with 5% H2SO4 solution, and then washed with water and saturated NaHCO3 respectively. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated to dryness. Compounds 6 and 7 were separated and purified by column chromatography.

[0051] Compound 6, white powder, 103.7 mg, yield 35.5%. Its structural formula and test data are as follows:

[0052]

[0053] R f 0.40 (petroleum:EtOAc, 1:1). 1 H NMR(400MHz,Chloroform-d)δ8.03 (d,J=7.1Hz,2H,H-2",H-6"),7.60(t,J=7.4Hz,1H,H-4"),7.48(t, J=7.7Hz,2H,H-3",H-5"),5.44(s,1H,H-9),5.12-4.95(m,3H,H-2',H-3',H-4'),4.75(d,J=7.8Hz,1H,H-1'),4.59(d,J=12.0Hz,1H,H-8),4.47 (d,J=12.0Hz,1H,H-8),4.18(dd,J=12.2,2.6Hz,1H,H-6'),4.13-4.08(m,1H,H-6'),3.69(qd,J=7.0,2.7Hz,2H,H-11),3.60(ddd,J=9.6,5 .3,2.6Hz,1H,H-5'),2.76(d,J=6.0Hz,1H,H-5),2.32(dd,J=10.7,6.9Hz,1H,H-6),2.02(dd,J=21.9,16.2Hz,14H,4COCH3,H-3),1.80(d,J= 10.6Hz,1H,H-6),1.35(s,3H,H-10),1.21(t,J=7.0Hz,3H,H-12).MS-ESI m / z Calcd for C33 H 40 O 15 Na[M+Na] + 699.67,found700.41.

[0054] Compound 7, white powder, 97.3 mg, yield 33.4%. Its structural formula and test data are as follows:

[0055]

[0056] R f 0.32 (petroleum:EtOAc, 1:1). 1 H NMR(400MHz,Chloroform-d)δ8.01 (d,J=6.9Hz,2H,H-2",H-6"),7.59(t,J=7.4Hz,1H,H-4"),7.45(t, J=7.8Hz,2H,H-3",H-5"),5.17(t,J=9.4Hz,1H,H-3'),5.11(s,1H,H-9),5.08-5.00(m,2H,H-2',H-4'),4.78(d,J=7.8Hz,1H,H-1'),4.57-4.47 (m,2H,H-8),4.19(dd,J=12.3,2.6Hz,1H,H-6'),4.12(dd,J=12.2,5.5Hz,1H,H-6'),3.73(dd,J=9.6,7.1Hz,1H,H-11),3.68-3.62(m,1H,H-5') ,3.51-3.41(m,1H,H-11),3.04(d,J=7.3Hz,1H,H-5),2.70(dd,J=11.1,7.4Hz,1H,H-6),2.65(d,J=4.1Hz,2H,H-3),2.09-1.96(m,13H,4COCH3, H-6),1.39(s,3H,H-10),1.10(t,J=7.0Hz,3H,H-12).MS-ESI m / z Calcd for C 33 H 40 O 15 Na[M+Na] + 699.67, found 700.46.

[0057] Embodiment 5

[0058] Compound 6 (63 mg, 0.09 mmol) was dissolved in anhydrous CH3OH (3 mL), and Et3N (0.30 mL, 2.3 mmol) was added. After reacting at room temperature for 24 hours, the reaction solution changed from turbid to clear. The reaction solution was then poured into water, extracted with CH2Cl2 three times, and washed with saturated NaCl three times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated. Compounds 8 and 9 were obtained by column chromatography.

[0059] Compound 8, white powder, 14.5 mg, yield 30.6%. Its structural formula and test data are as follows:

[0060]

[0061] R f 0.35 (CH2Cl2:CH3OH, 7:1). 1 H NMR (400MHz, Chloroform-d) δ7.94 (d, J=7.8Hz, 2H, H-2", H-6"), 7.50 (t, J=7.4Hz, 1H, H-4"), 7.36 (t, J= 7.6Hz,2H,H-3",H-5"),5.48(s,1H,H-9),4.66(q,J=12.1Hz,2H,H-8,H-1'),4.49(d,J=7.5Hz,1H,H-8),3.81(d,J=15.0Hz,2H,H-6'),3.60 (dt,J=19.5,9.5Hz,4H,H-3',H-4',H-11),3.43-3.36(m,1H,H-2'),3.28 (d,J=8.6Hz,1H,H-5'),2.67(d,J=6.5Hz,1H,H-6),2.37(dd,J=11.0,6.9Hz,1H,H-5),1.97(s,2H,H-3),1.79(d,J=10.7Hz,1H,H-6),1.33 (s,3H,H-10),1.17(t,J=7.0Hz,3H,H-12).MS-ESI m / z Calcd for C 25 H 32 O 11 Na [M+Na] + 531.52, found 531.23.

[0062] Compound 9, white powder, 26 mg, yield 71.5%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0063]

[0064] R f 0.07 (CH2Cl2:CH3OH, 7:1). 1 1H NMR (400 MHz, Acetone-d6) δ 5.21 (s, 1H, H-9), 4.65 (d, J = 7.7 Hz, 1H, H-8), 4.00 (d, J = 12.4 Hz, 1H, H-8), 3.90 (d, J = 12.3 Hz, 1H, H-1'), 3.81 (d, J = 11.5 Hz, 1H, H-6'), 3.67 - 3.58 (m, 3H, H-6', H-11), 3.46 (t, J = 8.7 Hz, 1H, H-5'), 3.35 - 3.30 (m, 2H, H-3', H-4'), 3.27 - 3.21 (m, 1H, H-2'), 2.49 (d, J = 8.6 Hz, 1H, H-6), 2.41 (dd, J = 10.6, 6.9 Hz, 1H, H-5), 1.98 (d, J = 17.3 Hz, 1H, H-3), 1.88 - 1.79 (m, 2H, H-6, H-3), 1.29 (s, 3H, H-10), 1.12 (t, J = 7.1 Hz, 3H, H-12). 13 13C NMR (101 MHz, Acetone-d6) δ 108.41 (C-4), 101.98 (C-9), 99.48 (C-1'), 88.96 (C-1), 86.10 (C-2), 78.14 (C-3'), 77.43 (C-5'), 74.77 (C-2'), 72.68 (C-11), 71.77 (C-4'), 62.99 (C-7), 59.51 (C-6'), 59.09 (C-8), 42.57 (C-3), 41.16 (C-5), 23.20 (C-12), 19.66 (C-6), 15.92 (C-10). MS-ESI m / z Calcd for C 18 H 28 O 10 Na [M+Na] + 427.41, found 427.56.

[0065] Example VI

[0066] Compound 7 (150 mg, 0.22 mmol) was dissolved in anhydrous CH3OH (5 mL), and Et3N (0.77 mL, 5.55 mmol) was added. After reacting at room temperature for 24 hours, the reaction solution changed from turbid to clear. The reaction solution was then poured into water, extracted with CH2Cl2 three times, and washed with saturated NaCl three times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated. Compounds 10 and 11 were obtained by column chromatography.

[0067] Compound 10, white powder, 30 mg, yield 26.8%. Its structural formula and test data are as follows:

[0068]

[0069] R f 0.34 (CH2Cl2:CH3OH, 7:1). 1 H NMR (400MHz, Chloroform-d) δ7.90 (d, J=7.4Hz, 2H, H-2", H-6"), 7.50 (t, J=7.5Hz, 1H, H-4"), 7.34 (t, J= 7.7Hz,2H,H-3",H-5"),5.12(s,1H,H-9),4.74(d,J=11.3Hz,1H,H-8),4.55(d,J=7.2Hz,2H,H-8,H-1'),3.83(s,2H,H-6'),3.64(p,J=9.7, 8.4Hz,3H,H-2',H-3',H-4'),3.48(s,1H,H-5'),3.39-3.31(m,2H,H-11), 2.96(d,J=7.1Hz,1H,H-6),2.80(d,J=10.2Hz,1H,H-5),2.60(q,J=18.2Hz,2H,H-3),2.00(d,J=10.8Hz,1H,H-6),1.39(s,3H,H-10),1.02 (t,J=7.0Hz,3H,H-12).MS-ESIm / z Calcd for C 18 H 28 O 10 Na[M+Na] + 531.52, found 531.95.

[0070] Compound 11, white powder, 60 mg, yield 67.5%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0071]

[0072] Rf 0.06 (CH2Cl2:CH3OH, 7:1). 1 1H NMR (400 MHz, Acetone-d6) δ 5.20 (s, 1H, H-9), 4.76 (d, J = 7.7 Hz, 1H, H-8), 4.02 (dd, J = 12.5, 3.6 Hz, 1H, H-6'), 3.85 - 3.78 (m, 1H, H-11), 3.76 - 3.58 (m, 3H, H-6', H-11, H-5'), 3.52 - 3.41 (m, 2H, H-3', H-4'), 3.37 - 3.25 (m, 3H, H-2', H-8, H-1'), 2.88 (d, J = 6.5 Hz, 1H, H-5), 2.74 (d, J = 17.9 Hz, 1H, H-6), 2.49 (d, J = 7.5 Hz, 1H, H-3), 2.38 (d, J = 17.9 Hz, 1H, H-3), 2.06 (d, J = 3.1 Hz, 1H, H-6), 1.34 (s, 3H, H-10), 1.06 (t, J = 7.1 Hz, 3H, H-12). 13 13C NMR (101 MHz, Acetone-d6) δ 205.35 (C-4), 103.66 (C-9), 98.89 (C-1'), 88.18 (C-1), 86.98 (C-2), 78.25 (C-3'), 77.50 (C-5'), 74.58 (C-2'), 71.79 (C-11), 65.24 (C-4'), 63.91 (C-7), 63.00 (C-8), 60.23 (C-6'), 49.48 (C-3), 47.23 (C-5), 26.63 (C-6), 20.77 (C-10), 15.09 (C-12). MS-ESI m / z Calcd for C 18 H 28 O 10 Na [M+Na] + 427.41, found 427.46.

[0073] Example VII

[0074] Paeoniflorin (160 mg, 0.33 mmol) was dissolved in n-propanol (n-propanol, 8 mL), and refluxed at 98°C for 40 min under the catalysis of Sc(CF3SO3)3 (164 mg, 0.33 mmol). The reaction solution was poured into water, extracted with EtOAc 3 times, and washed with saturated NaCl 3 times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated to dryness. After the organic phase was concentrated, a mixture of compounds 14 and 15 (143 mg, 82.3%) was obtained. Then, the mixture was added to Ac2O / Py (1: 1, 6 mL) and reacted at 0°C for 1 h for hydroxyacetylation. After the reaction solution was diluted with EtOAc, it was washed with 5% H2SO4 solution, and then washed with water and saturated NaHCO3 respectively. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated to dryness. Compounds 12 and 13 were purified and separated by column chromatography.

[0075] Compound 12, white powder, 57.2 mg, yield 30.7%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0076]

[0077] R f 0.42 (petroleum:EtOAc, 1:1). 1H NMR(400MHz,Chloroform-d)δ8.03 (d,J=7.0Hz,2H,H-2",H-6"),7.60(t,J=7.4Hz,1H,H-4"),7.48(t, J=7.7Hz,2H,H-3",H-5"),5.44(s,1H,H-9),5.11-4.95(m,3H,H-2',H-3',H-4'),4.75(d,J=7.8Hz,1H,H-1'),4.59(d,J=12.0Hz,1H,H-8),4.48 (d,J=12.0Hz,1H,H-8),4.18(dd,J=12.2,2.6Hz,1H,H-6'),4.11(dd, J=12.2,5.3Hz,1H,H-6'),3.63-3.53(m,3H,H-11,H-5'),2.77(d,J=6.8Hz,1H,H-5),2.32(dd,J=10.7,7.0Hz,1H,H-6),2.02(dd,J=21.4,16.8 Hz,14H,4COCH3,H-3),1.80(d,J=10.7Hz,1H,H-6),1.59(q,J=7.1Hz, 2H,H-12),1.35(s,3H,H-10),0.90(t,J=7.4Hz,3H,H-13). 13 C NMR(101 MHz,Chloroform-d)δ170.53,170.31,169.49,169.40(4CH3 C O),166.48(C-7"), 133.54(C-4"),129.72(C-2",C-6"),129.65(C-1"),128.73(C-3",C-5"),107.62(C-4),101.16(C-9),96.41(C-1'),88.43(C-1),85.64(C-2),73.04 (C-3'),71.81(C-5'),71.36(C-2'),69.83(C-11),68.47(C-4'),65.80(C-7),62.06(C-6'),60.25(C-8),41.60(C-3),40.90(C-5),23.21(C-12),22.31 (C-6),20.82,20.67,20.65×2(4 C H3CO),19.22(C-10),10.47(C-13).MS-ESI m / z Calcd forC 34 H 42 O 15 Na[M+Na]+ 713.70, found 712.87.

[0078] Compound 13, white powder, 73.4 mg, yield 39.4%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0079]

[0080] R f 0.34 (petroleum:EtOAc, 1:1). 1 H NMR(400MHz,Chloroform-d)δ8.01 (d,J=7.0Hz,2H,H-2",H-6"),7.59(t,J=7.5Hz,1H,H-4"),7.45(t, J=7.8Hz,2H,H-3",H-5"),5.17(t,J=9.4Hz,1H,H-3'),5.11(s,1H,H-9),5.04(dd,J=16.9,9.2Hz,2H,H-2",H-4"),4.78(d,J=7.9Hz, 1H,H-1'),4.56-4.47(m,2H,H-8),4.19(dd,J=12.2,2.5Hz,1H,H-6'),4.13(dd,J=12.2,5.5Hz,1H,H-6'),3.64(dt,J=9.6,6.7Hz,2H,H-11, H-5'),3.35(dt,J=9.3,6.4Hz,1H,H-11),3.05(d,J=7.4Hz,1H,H-5),2.73-2.67(m,1H,H-6),2.65(d,J=4.4Hz,2H,H-3),2.10-1.97(m,13H, 4COCH3,H-6),1.49(q,J=6.9Hz,2H,H-12),1.39(s,3H,H-10),0.83(t,J=7.4Hz,3H,H-13). 13 C NMR(101MHz,Chloroform-d)δ204.89(C-4),170.48, 170.32,169.51,169.42(4CH3 CO),166.46(C-7"),133.58(C-4"),129.78(C-2",C-6"),129.51(C-1"),128.66(C-3",C-5"),104.88(C -9),96.29(C-1'),87.93(C-1),85.78(C-2),72.98(C-3'),72.04(C-5'),71.51(C-2'),70.53(C-11), 68.40(C-4'),63.16(C-7),62.41(C-8),62.08(C-6'),48.91(C-3),46.91(C-5),26.28(C-6),22.69(C-12),20.81,20.73,20.68×2(4 C H3CO),20.47 (C-10),10.72(C-13).MS-ESI m / z Calcd forC 34 H 42 O 15 Na[M+Na] + 713.70, found 713.23.

[0081] Embodiment 8

[0082] Compound 12 (77 mg, 0.11 mmol) was dissolved in anhydrous CH3OH (3 mL), and Et3N (0.39 mL, 2.79 mmol) was added. After reacting at room temperature for 24 hours, the reaction solution changed from turbid to clear. The reaction solution was then poured into water, extracted with CH2Cl2 three times, and washed with saturated NaCl three times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated. Compound 14 was obtained by column chromatography.

[0083] Compound 14, white powder, 25.3 mg, yield 44.1%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0084]

[0085] R f 0.32 (CH2Cl2:CH3OH, 8:1). 11H NMR (400 MHz, Chloroform-d) δ 7.93 (d, J = 7.4 Hz, 2H, H-2", H-6"), 7.49 (t, J = 7.4 Hz, 1H, H-4"), 7.34 (t, J = 7.7 Hz, 2H, H-3", H-5"), 5.45 (s, 1H, H-9), 4.65 (q, J = 12.2 Hz, 2H, H-8, H-1'), 4.49 (d, J = 7.6 Hz, 1H, H-8), 3.78 (q, J = 11.8 Hz, 2H, H-6'), 3.57 (s, 2H, H-3', H-4'), 3.50 (t, J = 5.5 Hz, 2H, H-11), 3.39 (s, 1H, H-2'), 3.27 (s, 1H, H-5'), 2.66 (d, J = 6.4 Hz, 1H, H-6), 2.36 (s, 1H, H-5), 1.95 (s, 2H, H-3), 1.78 (d, J = 10.6 Hz, 1H, H-6), 1.54 (q, J = 7.2 Hz, 2H, H-12), 1.32 (s, 3H, H-10), 0.86 (t, J = 7.4 Hz, 3H, H-13). 13 13C NMR (101 MHz, Chloroform-d) δ 167.13 (C-7"), 133.47 (C-4"), 129.85 (C-2", C-6"), 129.61 (C-1"), 128.64 (C-3", C-5"), 107.70 (C-4), 101.25 (C-9), 98.82 (C-1'), 88.41 (C-1), 85.72 (C-2), 76.22 (C-3'), 75.72 (C-5'), 73.61 (C-2'), 70.12 (C-11), 69.70 (C-4'), 65.55 (C-7), 61.61 (C-6'), 60.93 (C-8), 41.78 (C-3), 40.33 (C-5), 23.23 (C-12), 19.53 (C-6), 19.53 (C-10), 10.49 (C-13). MS-ESI F m / z Calcd for C 26 H 34 O 11 Na [M+Na] + 545.55, found 545.48.

[0086] Example Nine

[0087] Compound 13 (150 mg, 0.22 mmol) was dissolved in anhydrous CH3OH (3 mL), and Et3N (0.75 mL, 5.4 mmol) was added. After reacting at room temperature for 24 hours, the reaction solution changed from turbid to clear. The reaction solution was then poured into water, extracted with CH2Cl2 three times, and washed with saturated NaCl three times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated. Compounds 15 and 16 were obtained by column chromatography.

[0088] Compound 15, white powder, 35.3 mg, yield 30.7%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0089]

[0090] R f 0.36 (CH2Cl2:CH3OH, 7:1). 1 H NMR (400MHz, Chloroform-d) δ7.90 (d, J=7.1Hz, 2H, H-2", H-6"), 7.50 (t, J=7.4Hz, 1H, H-4"), 7.33 (t, J= 7.7Hz,2H,H-3",H-5"),5.10(s,1H,H-9),4.75(d,J=11.7Hz,1H,H-8),4 .60-4.52(m,2H,H-8,H-1'),3.84(s,2H,H-6'),3.66(s,2H,H-3',H-4'), 3.53(m,2H,H-11),3.36(d,J=8.1Hz,1H,H-2'),3.27-3.20(m,1H,H-5'), 2.97(d,J=7.1Hz,1H,H-6),2.83-2.75(m,1H,H-5),2.59(q,J=18.2Hz,2H,H-3),1.99(d,J=10.9Hz,1H,H-6),1.41(d,J=10.2Hz,5H,H-10, H-12),0.77(t,J=7.4Hz,3H,H-13). 13C NMR(101MHz,Chloroform-d)δ205.24 (C-4),167.28(C-7"),133.70(C-4"),129.81(C-2",C-6"),129.33(C-1 "),128.62(C-3",C-5"),105.30(C-9),98.73(C-1'),87.97(C-1),85.82 (C-2),76.53(C-3'),75.89(C-5'),73.63(C-2'),70.42(C-11),69.52(C-4'),63.48(C-7),63.30(C-8) ,61.61(C-6'),48.85(C-3),46.98(C-5),26.59(C-6),22.69(C-12),20.72(C-10),10.73(C-13).MS-ESI m / z Calcd for C 26 H 34 O 11 Na [M+Na] + 545.55, found 545.16.

[0091] Compound 16, white powder, 46.7 mg, yield 40.6%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0092]

[0093] R f 0.05 (CH2Cl2:CH3OH, 7:1). 11H NMR (400 MHz, Acetone-d6) δ 5.19 (s, 1H, H-9), 4.76 (d, J = 7.7 Hz, 1H, H-8), 4.02 (d, J = 12.6 Hz, 1H, H-6'), 3.81 (dd, J = 11.8, 2.6 Hz, 1H, H-11), 3.71 (d, J = 12.6 Hz, 1H, H-6'), 3.64 - 3.55 (m, 2H, H-5', H-11), 3.48 (t, J = 8.7 Hz, 1H, H-3'), 3.40 - 3.32 (m, 3H, H-2', H-4', H-8), 3.27 (d, J = 9.0 Hz, 1H, H-1'), 2.90 (dd, J = 12.3, 7.6 Hz, 1H, H-5), 2.75 (d, J = 17.9 Hz, 1H, H-6), 2.49 (d, J = 7.4 Hz, 1H, H-3), 2.38 (d, J = 16.9 Hz, 1H, H-3), 2.09 (s, 1H, H-6), 1.47 (q, J = 6.9 Hz, 2H, H-12), 1.35 (s, 3H, H-10), 0.84 (t, J = 7.4 Hz, 3H, H-13). 13 13C NMR (101 MHz, Acetone-d6) δ 205.32 (C-4), 104.10 (C-9), 98.89 (C-1'), 88.21 (C-1), 86.96 (C-2), 78.17 (C-3'), 77.50 (C-5'), 74.53 (C-2'), 71.71 (C-11), 70.62 (C-4'), 65.34 (C-7), 62.92 (C-6'), 60.17 (C-8), 49.52 (C-3), 47.20 (C-5), 26.63 (C-6), 23.46 (C-12), 20.78 (C-10), 11.01 (C-13). MS-ESI m / z Calcd for C 19 H 30 O 10 Na[M + Na] + 441.44, found 441.83.

[0094] Example Ten

[0095] Paeoniflorin (170 mg, 0.35 mmol) was dissolved in iso-propanol (isopropanol, 8 mL), and refluxed at 83°C for 60 min under the catalysis of Sc(CF3SO3)3 (174 mg, 0.35 mmol). The reaction solution was poured into water, extracted with EtOAc 3 times, and washed with saturated NaCl 3 times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated to dryness. After the organic phase was concentrated, a mixture of compound 19 and compound 21 (123 mg, 67.3%) was obtained. Then, the mixture was added to Ac2O / Py (1:1, 6 mL) and reacted at 0°C for 1 h for hydroxyacetylation. After the reaction solution was diluted with EtOAc, it was washed with 5% H2SO4 solution, and then washed with water and saturated NaHCO3 respectively. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated to dryness. Compounds 17 and 18 were purified and separated by column chromatography.

[0096] Compound 17, white powder, 61 mg, yield 37.5%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0097]

[0098] R f 0.40 (petroleum: EtOAc, 1:1), mp 113-115°C. 1H NMR(400MHz,Chloroform-d) δ8.03(d,J=7.0Hz,2H,H-2",H-6"),7.60(t,J=7.4Hz,1H,H-4"),7.48(t,J=7.7Hz,2H,H-3",H-5"),5.42(s,1H,H-9),5.08-4.96(m,3H,H-2', H-3',H-4'),4.74(d,J=7.7Hz,1H,H-1'),4.59(d,J=11.9Hz,1H,H-8),4.49(d,J=12.0Hz,1H,H-8),4.17(dd,J=12.3,2.7Hz,1H,H-6'),4.11 (dd,J=12.2,5.6Hz,2H,H-6',H-11),3.62-3.56(m,1H,H-5'),2.73(d, J=6.7Hz,1H,H-5),2.32(dd,J=10.7,7.0Hz,1H,H-6),2.17(d,J=3.3Hz,1H,H-3),2.07,2.01,1.97(13H,4COCH3,H-3),1.80(d,J=10.6Hz, 1H,H-6),1.34(s,3H,H-10),1.18(dd,J=6.2,2.7Hz,6H,H-12,H-13). 13 C NMR(101MHz,Chloroform-d)δ170.54,170.32,169.50,169.40(4CH3 C O), 166.50(C-7"),133.55(C-4"),129.73(C-2",C-6",C-1"),128.76(C-3",C-5"),107.81(C-4),101.15(C-9),96.44(C-1'),88.39(C-1),85.70(C-2),73.09 (C-3'),71.83(C-5'),71.39(C-2'),69.57(C-11),68.51(C-4'),67.44(C-7),62.08(C-6'),60.34(C-8),42.14(C-3),41.88(C-5),24.26(C-12),24.13 (C-13),22.40(C-6),20.83,20.70,20.68,20.66(4 C H3CO),19.26(C-10).MS-ESI m / z Calcd for C 34 H 42 O 15 Na[M+Na]+ 713.70, found 714.19.

[0099] Compound 18, white powder, 62 mg, yield 38.1%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0100]

[0101] R f 0.36 (petroleum: EtOAc, 1:1), mp 147-149°C. 1 H NMR(400MHz,Chloroform-d)δ8.01(d,J=7.0Hz,2H,H-2",H-6"),7.58(t,J=7.5Hz,1 H,H-4"),7.44(t,J=7.6Hz,2H,H-3",H-5"),5.20(s,1H,H-9),5.15(d,J=9.4Hz,1H, H-2'),5.07-4.99(m,2H,H-3',H-4'),4.77(d,J=7.9Hz,1H,H-1'),4.51 (q,J=11.8Hz,2H,H-8),4.18(dd,J=12.2,2.4Hz,1H,H-6'),4.12(dd,J=12.2,5.3Hz,1H,H-6'),3.91(p,J=6.2Hz,1H,H-11),3.68-3.62(m,1H ,H-5'),3.03(d,J=7.3Hz,1H,H-5),2.67(m,3H,H-6,H-3),2.08,2.05,2.02,1.99(13H,4COCH3,H-3),1.37(s,3H,H-10),1.11(d,J=6.2Hz,3H, H-12),1.00(d,J=6.1Hz,3H,H-13). 13 C NMR (101 MHz, Chloroform-d)δ 13 C NMR(101MHz,Chloroform-d)δ205.05(C-4),170.48,170.33,169.51,169.43 (4CH3 CO),166.48(C-7"),133.58(C-4"),129.82(C-2",C-6"),129.50(C-1"), 128.65(C-3",C-5"),102.42(C-9),96.29(C-1'),87.91(C-1),85.61(C-2), 73.00(C-3'),72.04(C-5'),71.53(C-2'),70.13(C-11),68.42(C-4'),62.90 (C-7),62.40(C-8),62.10(C-6'),49.01(C-3),46.97(C-5),26.26(C-6),22.54(C-12),21.32(C-13),20.82,20.75,20.69×2(4 C H3CO),20.54(C-10). MS-ESI m / z Calcd forC 34 H 42 O 15 Na[M+Na] + 713.70, found 714.23.

[0102] Embodiment 11

[0103] Compound 17 (64 mg, 0.09 mmol) was dissolved in anhydrous CH3OH (3 mL), and Et3N (0.30 mL, 2.3 mmol) was added. After reacting at room temperature for 24 hours, the reaction solution changed from turbid to clear. The reaction solution was then poured into water, extracted with CH2Cl2 three times, and washed with saturated NaCl three times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated. Compounds 19 and 20 were obtained by column chromatography.

[0104] Compound 19, white powder, 24.7 mg, yield 52.5%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0105]

[0106] R f 0.39 (CH2Cl2:CH3OH, 7:1). 1H NMR (400MHz, Chloroform-d) δ7.94 (d, J=6.9Hz, 2H, H-2", H-6"), 7.50 (t, J=7.4Hz, 1H, H-4"), 7.36 (t, J= 7.6Hz,2H,H-3",H-5"),5.46(s,1H,H-9),4.70-4.60(m,2H,H-8,H-1'), 4.49(d,J=7.4Hz,1H,H-8),4.05(p,J=6.1,5.6Hz,1H,H-11),3.79(d,J=9.3Hz,2H,H-6'),3.54(d,J=10.6Hz,2H,H-3',H-4'),3.39(s,1H, H-2'),3.26(d,J=8.6Hz,1H,H-5'),2.64(d,J=6.6Hz,1H,H-6),2.37 (dd,J=10.9,6.9Hz,1H,H-5),1.96(s,2H,H-3),1.79(d,J=10.7Hz,1H,H-6),1.32(s,3H,H-10),1.14(d,J=6.1Hz,6H,H-12,H-13). 13 C NMR (101MHz,Chloroform-d)δ167.11(C-7"),133.45(C-4"),129.84(C-2",C-6"), 129.68(C-1"),128.63(C-3",C-5"),107.87(C-4),101.19(C-9),98.91(C-1'), 88.41(C-1),85.76(C-2),76.39(C-3'),75.73(C-5'),73.51(C-2'),69.84(C-11),69.53(C-4'),67.19(C-7),61 .69(C-6'),60.92(C-8),42.34(C-3),41.21(C-5),24.25(C-12),24.13(C-13),22.80(C-6),19.55(C-10).MS-ESI m / z Calcdfor C 26 H 34 O 11 Na[M+Na] + 545.55, found 545.86.

[0107] Compound 20, white powder, 12.2 mg, yield 32.4%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0108]

[0109] R f 0.08 (CH2Cl2:CH3OH, 7:1). 1 1H NMR (400 MHz, Acetone-d6) δ 5.20 (s, 1H, H-9), 4.65 (d, J = 7.7 Hz, 1H, H-8), 3.99 (d, J = 12.3 Hz, 1H, H-8), 3.88 (d, J = 12.4 Hz, 1H, H-1'), 3.81 (dd, J = 11.6, 2.1 Hz, 1H, H-6'), 3.61 (dd, J = 11.6, 5.3 Hz, 1H, H-11), 3.43 (t, J = 8.3 Hz, 1H, H-5'), 3.37 - 3.30 (m, 3H, H-3', H-4', H-6'), 3.25–3.20 (m, 1H, H-2'), 2.46–2.37 (m, 2H, H-5, H-6), 2.02 (d, J = 12.3 Hz, 1H, H-3), 1.87–1.79 (m, 2H, H-3, H-6), 1.28 (s, 3H, H-10), 1.11 (dd, J = 6.1, 1.6 Hz, 6H, H-12, H-13). 13 13C NMR (101 MHz, Acetone-d6) δ 108.58 (C-4), 101.96 (C-9), 99.47 (C-1'), 88.88 (C-1), 86.07 (C-2), 78.27 (C-3'), 77.46 (C-5'), 74.81 (C-2'), 72.43 (C-11), 71.82 (C-4'), 66.91 (C-7), 63.04 (C-6'), 59.12 (C-8), 43.07 (C-3), 41.91 (C-5), 24.55 (C-12), 24.39 (C-13), 23.16 (C-6), 19.65 (C-10). MS-ESI m / z Calcd for C 19 H 30 O 10 Na[M+Na] + 441.44, found 441.20.

[0110] Example XII

[0111] Compound 18 (64 mg, 0.09 mmol) was dissolved in anhydrous CH3OH (3 mL), and Et3N (0.30 mL, 2.3 mmol) was added. After reacting at room temperature for 24 hours, the reaction solution changed from turbid to clear. The reaction solution was then poured into water, extracted with CH2Cl2 three times, and washed with saturated NaCl three times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated. Compounds 21 and 22 were obtained by column chromatography.

[0112] Compound 21, white powder, 18.3 mg, yield 38.9%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0113]

[0114] R f 0.34 (CH2Cl2:CH3OH, 7:1). 1 H NMR (400MHz, Chloroform-d) δ7.92 (d, J=7.3Hz, 2H, H-2", H-6"), 7.50 (t, J=7.5Hz, 1H, H-4"), 7.34 (t, J= 7.7Hz,2H,H-3",H-5"),5.21(s,1H,H-9),4.78(d,J=11.7Hz,1H,H-8),4.58-4.51(m,2H,H-8,H-1'),3.81(dd,J=11.2,5.1Hz,3H,H-6',H-11), 3.68-3.61(m,2H,H-3',H-4'),3.49(s,1H,H-2'),3.35(s,1H,H-5'),2.95 (d,J=7.0Hz,1H,H-6),2.78(t,J=9.3Hz,1H,H-5),2.67-2.53(m,2H,H-3),1.98(d,J=10.8Hz,1H,H-6),1.38(s,3H,H-10),1.05(d,J=6.2 Hz,3H,H-12),0.90(d,J=6.1Hz,3H,H-13). 13C NMR(101MHz,Chloroform-d) δ205.42(C-4),167.31(C-7"),133.85(C-4"),129.89(C-2",C-6"),129.33( C-1"),128.64(C-3",C-5"),102.97(C-9),98.73(C-1'),87.86(C-1),85.67 (C-2),76.47(C-3'),75.93(C-5'),73.69(C-2'),70.22(C-11),69.72(C-4'), 63.45(C-7),63.12(C-8),61.67(C-6'),49.01(C-3),45.80(C-5),26.76(C-6), 22.58(C-12),21.39(C-13),20.78(C-10).MS-ESI m / z Calcd for C 26 H 34 O 11 Na [M+Na] + 545.55, found 545.60.

[0115] Compound 22, white powder, 14.5 mg, yield 38.5%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0116]

[0117] R f 0.04 (CH2Cl2:CH3OH, 7:1). 11H NMR (400 MHz, Acetone-d6) δ 5.32 (s, 1H, H-9), 4.76 (d, J = 7.7 Hz, 1H, H-8), 4.01 (d, J = 12.5 Hz, 1H, H-6'), 3.81 (dd, J = 11.7, 2.6 Hz, 1H, H-11), 3.70 (d, J = 12.5 Hz, 1H, H-6'), 3.62 (dd, J = 11.7, 5.6 Hz, 1H, H-5'), 3.48 (t, J = 8.6 Hz, 1H, H-3), 3.40 - 3.34 (m, 2H, H-2', H-4'), 3.33 - 3.25 (m, 2H, H-8, H-1'), 2.89 (dd, J = 11.2, 7.4 Hz, 1H, H-5), 2.74 (d, J = 18.2 Hz, 1H, H-6), 2.47 - 2.38 (m, 2H, H-3), 2.06 (s, 1H, H-6), 1.34 (s, 3H, H-10), 1.05 (dd, J = 7.8, 6.2 Hz, 6H, H-12, H-13). 13 13C NMR (101 MHz, Acetone-d6) δ 205.48 (C-4), 101.61 (C-9), 98.87 (C-1'), 87.72 (C-1), 86.89 (C-2), 78.16 (C-3'), 77.48 (C-5'), 74.52 (C-2'), 71.70 (C-11), 69.93 (C-4'), 65.09 (C-7), 62.91 (C-6'), 60.07 (C-8), 49.59 (C-3), 47.24 (C-5), 26.69 (C-6), 22.91 (C-12), 21.64 (C-13), 20.83 (C-10). MS-ESI m / z Calcd for C 19 H 30 O 10 Na[M + Na] + 441.44, found 441.32.

[0118] Example Thirteen

[0119] Paeoniflorin (160 mg, 0.33 mmol) was dissolved in butyl alcohol (butanol, 8 mL), and refluxed at 118°C for 45 min under the catalysis of Sc(CF3SO3)3 (164 mg, 0.33 mmol). The reaction solution was poured into water, extracted with EtOAc 3 times, and washed with saturated NaCl 3 times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated to dryness. After the organic phase was concentrated, a mixture of compound 25 and compound 26 (135 mg, 75.6%) was obtained. Then, the mixture was added to Ac2O / Py (1:1, 6 mL) and reacted at 0°C for 1 h for hydroxyacetylation. After the reaction solution was diluted with EtOAc, it was washed with 5% H2SO4 solution, and then washed with water and saturated NaHCO3 respectively. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated to dryness. Compounds 23 and 24 were purified and separated by column chromatography.

[0120] Compound 23, white powder, 31.4 mg, yield 17.7%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0121]

[0122] R f 0.39 (petroleum: EtOAc, 1:1). 1H NMR(400MHz,Chloroform-d)δ8.03 (d,J=7.1Hz,2H,H-2",H-6"),7.60(d,J=14.9Hz,1H,H-4"),7.47(t, J=7.7Hz,2H,H-3",H-5"),5.44(s,1H,H-9),5.12-4.96(m,3H,H-2',H-3',H-4'),4.75(d,J=7.8Hz,1H,H-1'),4.59(d,J=12.0Hz,1H,H-8),4.48 (d,J=12.0Hz,1H,H-8),4.18(dd,J=12.2,2.6Hz,1H,H-6'),4.11(dd,J=12.2,5.3Hz,1H,H-6'),3.61(tt,J=5.3,2.8Hz,3H,H-11,H-5'),2.77(d,J=8.5Hz,1H,H-5),2.32(dd,J=10.7,6.9Hz,1H,H-6),2.07,2.03,2.02,1.98(m,14H,4COCH3,H-3),1.79(d,J=10.7Hz,1H,H-6),1.58-1.50 (m,2H,H-13),1.35(m,3H,H-12,H-10),0.90(t,J=7.4Hz,3H,H-14). 13 C NMR(101MHz,Chloroform-d)δ170.58,170.36,169.53,169.43(4CH3 C O), 166.52(C-7"),133.58(C-4"),129.75(C-2",C-6"),129.67(C-1"),128.76(C-3",C-5"),107.65(C-4),101.20(C-9),96.44(C-1'),88.45(C-1),85.67(C-2),73.08(C-3'),71.84(C-5'),71.39(C-2'),69.86(C-11),68.49(C-4'),64.03(C-7),62.09(C-6'),60.27(C-8),41.63(C-3),40.92(C-5),32.01 (C-12),22.34(C-6),20.86×2,20.72×2(4 C H3CO),20.69(C-10),19.28(C-13), 13.94(C-14).MS-ESI m / z Calcd forC 35 H 44 O 15Na[M+Na] + 727.72, found 728.19.

[0123] Compound 24, white powder, 72.6 mg, yield 40.9%. Its structural formula and test data are as follows:

[0124]

[0125] R f 0.35 (petroleum:EtOAc, 1:1). H NMR(400MHz,Chloroform-d)δ8.01 (d,J=8.5Hz,2H,H-2",H-6"),7.59(t,J=7.4Hz,1H,H-4"),7.45(t, J=7.7Hz,2H,H-3",H-5"),5.17(t,J=9.4Hz,1H,H-2'),5.10(s,1H,H-9),5.08-5.00(m,2H,H-3',H-4'),4.78(d,J=7.9Hz,1H,H-1'),4.56-4.47 (m,2H,H-8),4.19(dd,J=12.2,2.5Hz,1H,H-6'),4.13(dd,J=12.2,5.4 Hz,1H,H-6'),3.72-3.62(m,2H,H-11,H-5'),3.37(dt,J=9.5,6.4Hz,1H,H-11),3.04(d,J=7.3Hz,1H,H-5),2.73-2.67(m,1H,H-6),2.65(d,J= 5.7Hz,2H,H-3,H-6),2.08,2.05,2.03,2.00(m,13H,4COCH3,H-3),1.44(dt, J=8.8,6.2Hz,2H,H-13),1.39(s,3H,H-10),1.26(d,J=7.8Hz,2H,H-12), 0.83 (t, J = 7.3 Hz, 3H, H-14). 13 C NMR(101MHz,Chloroform-d)δ204.90(C-4), 170.52,170.37,169.54,169.46(4CH3 CO),166.50(C-7"),133.61(C-4"),129.83 (C-2",C-6"),129.53(C-1"),128.68(C-3",C-5"),104.94(C-9),96.32(C -1'),87.96(C-1),85.77(C-2),73.01(C-3'),72.08(C-5'),71.54(C-2') ,68.64(C-11),68.41(C-4'),63.15(C-7),62.43(C-8),62.11(C-6'),48. 94(C-3),46.92(C-5),31.48(C-12),26.31(C-6),20.85,20.77,20.72×2(4 C H3CO), 20.51(C-10),19.32(C-13),13.92(C-14).MS-ESI m / z Calcd for C 35 H 44 O 15 Na [M+Na] + 727.72, found 728.57.

[0126] Embodiment 14

[0127] Compound 23 (60 mg, 0.09 mmol) was dissolved in anhydrous CH3OH (3 mL), and Et3N (0.30 mL, 2.3 mmol) was added. After reacting at room temperature for 24 hours, the reaction solution changed from turbid to clear. The reaction solution was then poured into water, extracted with CH2Cl2 three times, and washed with saturated NaCl three times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated. Compound 25 was obtained by column chromatography.

[0128] Compound 25, white powder, 21.7 mg, yield 44.9%. Its structural formula and test data are as follows:

[0129]

[0130] R f 0.34 (CH2Cl2:CH3OH, 7:1). 11H NMR (400 MHz, Chloroform-d) δ 7.92 (d, J = 7.2 Hz, 2H, H-2", H-6"), 7.48 (t, J = 7.5 Hz, 1H, H-4"), 7.34 (t, J = 7.6 Hz, 2H, H-3", H-5"), 5.46 (s, 1H, H-9), 4.66 (t, J = 8.5 Hz, 2H, H-8, H-1'), 4.50 (d, J = 7.2 Hz, 1H, H-8), 3.79 (d, J = 10.4 Hz, 2H, H-6'), 3.62 - 3.47 (m, 4H, H-3', H-4', H-11), 3.41 (s, 1H, H-2'), 3.29 (s, 1H, H-5'), 2.66 (d, J = 6.3 Hz, 1H, H-6), 2.38 (d, J = 10.0 Hz, 1H, H-5), 1.94 (s, 2H, H-3), 1.78 (d, J = 10.4 Hz, 1H, H-6), 1.50 (p, J = 6.9 Hz, 2H, H-12), 1.36 - 1.27 (m, 5H, H-10, H-13), 0.87 (t, J = 7.3 Hz, 3H, H-14). 13 13C NMR (101 MHz, Chloroform-d) δ 167.12 (C-7"), 133.45 (C-4"), 129.85 (C-2", C-6"), 129.64 (C-1"), 128.62 (C-3", C-5"), 107.72 (C-4), 101.25 (C-9), 98.90 (C-1'), 88.48 (C-1), 85.73 (C-2), 76.38 (C-3'), 75.75 (C-5'), 73.57 (C-2'), 70.10 (C-11), 69.53 (C-4'), 63.74 (C-7), 61.67 (C-6'), 60.94 (C-8), 41.81 (C-3), 40.27 (C-5), 32.01 (C-12), 29.84 (C-6), 19.55 (C-10), 19.26 (C-13), 13.94 (C-14). MS-ESI m / z Calcd for C 27 H 36 O 11 Na[M+Na] + 558.57, found 559.18.

[0131] Example XV

[0132] Compound 24 (80 mg, 0.11 mmol) was dissolved in anhydrous CH3OH (3 mL), and Et3N (0.40 mL, 2.84 mmol) was added. After reacting at room temperature for 24 hours, the reaction solution changed from turbid to clear. The reaction solution was then poured into water, extracted with CH2Cl2 three times, and washed with saturated NaCl three times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated. Compounds 26 and 27 were obtained by column chromatography.

[0133] Compound 26, white powder, 25.1 mg, yield 42.5%. Its structural formula and test data are as follows:

[0134]

[0135] R f 0.35 (CH2Cl2:CH3OH, 7:1). 1 H NMR(400MHz,Chloroform-d)δ7.90(d, J=7.2Hz,2H,H-2",H-6"),7.50(t,J=7.5Hz,1H,H-4"),7.33(t,J=7.7Hz,2H,H-3",H-5"),5.09(s,1H,H-9),4.75(d,J=11.7Hz,1H,H-8), 4.59-4.51(m,2H,H-8,H-1'),3.84(s,2H,H-6'),3.66(d,J=6.9Hz,2H, H-11),3.58(t,J=7.9Hz,1H,H-3'),3.50(s,1H,H-4'),3.38-3.34(m,1H,H-2'),3.25(q,J=7.3,6.5Hz,1H,H-5'),2.97(d,J=7.1Hz,1H,H-6), 2.79(d,J=9.6Hz,1H,H-5),2.67-2.49(m,2H,H-3),1.99(d,J=10.8Hz, 1H,H-6),1.36(d,J=20.3Hz,5H,H-10,H-12),1.18(q,J=7.5Hz,2H,H-13),0.77(t,J=7.3Hz,3H,H-14). 13C NMR(101MHz,Chloroform-d)δ205.17 (C-4),167.30(C-7"),133.71(C-4"),129.85(C-2",C-6"),129.37(C-1"), 128.63(C-3",C-5"),105.35(C-9),98.74(C-1'),87.98(C-1),85.82(C-2), 76.55(C-3'),75.92(C-5'),73.69(C-2'),69.62(C-11),68.52(C-4'),63.4 9(C-7),63.30(C-8),61.64(C-6'),48.87(C-3),46.99(C-5),31.48(C-12), 26.62(C-6),20.74(C-10),19.29(C-13),13.90(C-14).MS-ESI m / z Calcd for C 27 H 36 O 11 Na[M+Na] + 558.57, found 559.13.

[0136] Compound 27, white powder, 17.8 mg, yield 37.4%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0137]

[0138] R f 0.06 (CH2Cl2:CH3OH, 7:1). 11H NMR (400 MHz, Acetone-d6) δ 5.18 (s, 1H, H-9), 4.76 (d, J = 7.7 Hz, 1H, H-8), 4.02 (d, J = 12.5 Hz, 1H, H-6'), 3.81 (dd, J = 11.7, 2.6 Hz, 1H, H-11), 3.72 (d, J = 12.6 Hz, 1H, H-6'), 3.66 - 3.59 (m, 2H, H-11, H-5'), 3.49 - 3.44 (m, 1H, H-3'), 3.39 - 3.33 (m, 2H, H-2', H-4'), 3.32 - 3.25 (m, 2H, H-8, H-1'), 2.89 (dd, J = 11.1, 7.6 Hz, 1H, H-5), 2.74 (d, J = 16.7 Hz, 1H, H-6), 2.49 (d, J = 7.4 Hz, 1H, H-3), 2.38 (d, J = 17.9 Hz, 1H, H-3), 2.09 (s, 1H, H-6), 1.47 - 1.39 (m, 2H, H-12), 1.34 (s, 3H, H-10), 1.33 - 1.28 (m, 2H, H-13), 0.87 (t, J = 7.3 Hz, 3H, H-14). 13 13C NMR (101 MHz, Acetone-d6) δ 205.30 (C-4), 104.11 (C-9), 98.88 (C-1'), 88.19 (C-1), 86.95 (C-2), 78.17 (C-3'), 77.49 (C-5'), 74.50 (C-2'), 71.72 (C-11), 68.59 (C-4'), 65.33 (C-7), 62.93 (C-6'), 60.19 (C-8), 49.52 (C-3), 47.19 (C-5), 32.32 (C-12), 26.65 (C-6), 20.77 (C-10), 19.82 (C-13), 14.10 (C-14). MS-ESI m / z Calcd for C 20 H 32 O 10 Na [M+Na] + 455.47, found 455.20.

[0139] Example XVI

[0140] Paeoniflorin (160 mg, 0.33 mmol) was dissolved in 2-butyl alcohol (2-butanol, 8 mL), and refluxed at 99.5 ° C for 35 min under the catalysis of Sc(CF3SO3)3 (164 mg, 0.33 mmol). The reaction solution was poured into water, extracted with EtOAc 3 times, and washed with saturated NaCl 3 times. The organic phase was dried over anhydrous Na2SO4, concentrated and evaporated to dryness. After the organic phase was concentrated, a mixture of compound 30 and compound 32 (140.7 mg, 75.6%) was obtained. Then, the mixture was added to Ac2O / Py (1:1, 6 mL) and reacted at 0 ° C for 1 h for hydroxyacetylation. After diluting the reaction solution with EtOAc, it was washed with 5% H2SO4 solution, and then washed with water and saturated NaHCO3 respectively. The organic phase was dried over anhydrous Na2SO4, concentrated and evaporated to dryness. Compounds 28 and 29 were purified and separated by column chromatography.

[0141] Compound 28, white powder, 68 mg, yield 37.0%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0142]

[0143] R f 0.40 (petroleum:EtOAc, 1:1). 1H NMR(400MHz,Chloroform-d)δ8.03 (d,J=8.1Hz,2H,H-2",H-6"),7.60(t,J=7.4Hz,1H,H-4"),7.48(t, J=7.7Hz,2H,H-3",H-5"),5.42(s,1H,H-9),5.11-4.95(m,3H,H-2',H-3',H-4'),4.74(d,J=7.7Hz,1H,H-1'),4.59(d,J=11.9Hz,1H,H-8),4.49 (d,J=11.9Hz,1H,H-8),4.19-4.08(m,2H,H-6'),3.85(dq,J=12.1,6.1Hz,1H,H-11),3.59(dq,J=8.1,5.2,4.2Hz,1H,H-5'),2.73(t,J=5.9 Hz,1H,H-5),2.32(dt,J=12.0,6.4Hz,1H,H-6),2.07,2.02,2.01,1.97 (14H,4COCH3,H-3),1.80(dd,J=10.6,4.0Hz,1H,H-6),1.57-1.48(m,1H, H-12),1.43(dt,J=14.4,7.3Hz,1H,H-12),1.34(s,3H,H-10),1.19-1.14(m,3H,H-13),0.86(q,J=7.1Hz,3H,H-14). 13 C NMR(101MHz,Chloroform-d) δ170.56,170.34,169.52,169.42(4CH3 C O),166.51(C-7"),133.57(C-4"), 129.74(C-2",C-6"),128.77(C-1",C-3",C-5"),107.91,107.82(C-4),101.24,101.08(C-9),96.48(C-1'),88.42(C-1),85.71(C-2),73.11(C-3'),72.42, 72.27(C-11),71.86(C-5'),71.43,71.41(C-2'),69.67,69.50(C-7),68.55(C-4'),62.14(C-6'),60.37(C-8),42.14(C-3),41.48(C-5),30.70,30.65 (C-12),22.42(C-6),21.84,21.67(C-13),20.83,20.72,20.69,20.68(4 CH3CO), 19.29(C-10),10.23,10.04(C-14).MS-ESI m / z Calcd for C 35 H 44 O 15 Na[M+Na] + 727.72, found 728.43.

[0144] Compound 29, white powder, 50.7 mg, yield 27.6%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0145]

[0146] R f 0.37 (petroleum: EtOAc, 1:1). 1 H NMR(400MHz,Chloroform-d)δ8.01 (d,J=8.0Hz,2H,H-2",H-6"),7.58(t,J=7.4Hz,1H,H-4"),7.44(t, J=7.6Hz,2H,H-3",H-5"),5.21(d,J=10.7Hz,1H,H-9),5.16(dt,J=9.4,4.7Hz,1H,H-2'),5.03(qd,J=9.4,2.1Hz,2H,H-3',H-4'),4.77(d, J=7.8Hz,1H,H-1'),4.55-4.46(m,2H,H-8),4.20-4.09(m,2H,H-6'),3.69 (dq,J=23.0,7.1,6.6Hz,2H,H-11,H-5'),3.03(d,J=7.0Hz,1H,H-5),2.68(d,J=12.3Hz,3H,H-3,H-6),2.08,2.07,2.05,2.02,1.99(m,13H, 4COCH3,H-3),1.56-1.40(m,2H,H-12),1.37(s,3H,H-10),1.11(d,J=6.2 Hz,1H,H-13),0.97(d,J=6.1Hz,2H,H-13),0.83(t,J=7.5Hz,2H,H-14),0.72(t,J=7.4Hz,1H,H-14). 13 C NMR(101MHz,Chloroform-d)δ205.16, 205.08(C-4),170.50,170.34,169.52,169.45(4CH3 CO),166.53,166.49(C-7"),133.60(C-4"),129.84(C-2",C-6"),129.50(C-1"),128.66(C -3",C-5"),103.70,102.24(C-9),96.31(C-1'),88.06,87.94(C-1),85.64,85.59(C-2), 76.19,74.89(C-11),73.03(C-2'),72.06(C-5'),71.55(C-3'),68.45(C-4' ),63.00,62.93(C-7),62.47,62.45(C-8),62.13(C-6'),49.06,49.03(C-6), 46.93(C-5),29.38,28.58(C-12),26.41,26.31(C-3),20.83,20.76,20.74, 20.69(4 C H3CO),20.58(C-10),19.77,18.04(C-13),9.52,9.34(C-14).MS-ESI m / z Calcd for C 35 H 44 O 15 Na[M+Na] + 727.72, found 728.25.

[0147] Embodiment 17

[0148] Compound 28 (90 mg, 0.12 mmol) was dissolved in anhydrous CH3OH (3 mL), and Et3N (0.44 mL, 3.20 mmol) was added. After reacting at room temperature for 24 hours, the reaction solution changed from turbid to clear. The reaction solution was then poured into water, extracted with CH2Cl2 three times, and washed with saturated NaCl three times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated. Compounds 30 and 31 were obtained by column chromatography.

[0149] Compound 30, white powder, 31.8 mg, yield 49.4%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0150]

[0151] R f 0.36 (CH2Cl2:CH3OH, 7:1). 1H NMR(400MHz,Chloroform-d)δ7.93(d, J=8.5Hz,2H,H-2",H-6"),7.48(t,J=7.5Hz,1H,H-4"),7.34(t,J= 6.9Hz,2H,H-3",H-5"),5.45(s,1H,H-9),4.65(q,J=12.1Hz,2H,H-8,H-1'),4.49(d,J=7.5Hz,1H,H-8),3.85-3.73(m,3H,H-6',H-11),3.61 (m,2H,H-3',H-4'),3.46-3.38(m,1H,H-2'),3.28(d,J=8.2Hz,1H,H-5'), 2.63(d,J=6.4Hz,1H,H-6),2.35(t,J=7.9Hz,1H,H-5),2.01-1.88(m,2H,H-3),1.76(d,J=10.7Hz,1H,H-6),1.53-1.37(m,2H,H-12),1.31(s, 3H,H-10),1.11(d,J=6.1Hz,3H,H-13),0.82(q,J=5.7Hz,3H,H-14). 13 C NMR(101MHz,Chloroform-d)δ167.07(C-7"),133.42(C-4"),129.82(C-2", C-6"),129.69(C-1"),128.61(C-3",C-5"),107.92,107.88(C-4),101.23,101.14(C-9),98.89(C-1'),88.40,88.37(C-1),85.78,85.74(C-2),76.33(C-3'),75.73(C-5'),73.58(C-2'),72.09,72.03(C-11),69.96,69.80(C-7),69.65(C-4'),61.68(C-6'),60.93(C-8),42.64,42.31(C-3),41.33,40.89 (C-5),30.67,30.63(C-12),22.75(C-6),21.83,21.57(C-13),19.53(C-10),10.19,10.03(C-14).MS-ESI m / zCalcd for C 27 H 36 O 11 Na[M+Na] + 558.57,found 559.07.

[0152] Compound 31, white powder, 20.4 mg, yield 47.2%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0153]

[0154] R f 0.06 (CH2Cl2:CH3OH, 7:1). 1 H NMR (400MHz, Acetone-d6) δ5.20 (d, J = 3.1Hz, 1H, H-9), 4.66 (d, J = 7.7Hz, 1H, H-8), 3.99 (d, J = 12.4Hz, 1H, H-8),3.89(d,J=8.3Hz,1H,H-1'),3.80(d,J=11.5Hz,1H,H-6'),3.62(dd,J=12.1,4.3Hz,1H,H-6'),3.52(d,J=7.2Hz,1H,H-11),3.45(d, J=8.4Hz,1H,H-5'),3.33(d,J=5.3Hz,2H,H-3',H-4'),3.24(t,J=8.3Hz,1H,H-2'),2.51-2.37(m,2H,H-6,H-5),2.08(d,J=5.0Hz,2H,H-3), 1.82(d,J=10.3Hz,1H,H-6),1.43(m,2H,H-12),1.29(s,3H,H-10),1.10(dd,J=6.1,2.9Hz,3H,H-13),0.85(td,J=7.5,3.2Hz,3H,H-14). 13 C NMR(101MHz,Acetone-d6)δ128.71,108.66(C-4),102.05,101.80(C-9),99.49 (C-1'),88.94(C-1),86.08(C-2),78.08(C-3'),77.44(C-5'),74.71(C-2'), 72.41,72.33(C-11),71.80,71.72,71.63(C-7),62.95(C-4'),59.15(C-6') ,59.04(C-8),43.46,43.05(C-3),42.29,41.48(C-5),31.33,31.25(C-12), 23.18(C-6),22.19,22.02(C-13),19.69(C-10),10.29,10.14(C-14).MS-ESI m / z Calcd forC 20 H 32 O10 Na[M+Na] + 455.47, found 455.30.

[0155] Embodiment 18

[0156] Compound 29 (80 mg, 0.11 mmol) was dissolved in anhydrous CH3OH (3 mL), and Et3N (0.40 mL, 2.84 mmol) was added. After reacting at room temperature for 24 hours, the reaction solution changed from turbid to clear. The reaction solution was then poured into water, extracted with CH2Cl2 three times, and washed with saturated NaCl three times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated. Compounds 32 and 33 were obtained by column chromatography.

[0157] Compound 32, white powder, 27.5 mg, yield 46.6%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0158]

[0159] R f 0.37 (CH2Cl2:CH3OH, 7:1). 1 H NMR (400MHz, Chloroform-d) δ7.92 (d, J=8.0Hz, 2H, H-2", H-6"), 7.50 (t, J=7.5Hz, 1H, H-4"), 7.34 (t, J= 7.7Hz,2H,H-3",H-5"),5.22(d,J=13.5Hz,1H,H-9),4.77(t,J=12.3 Hz,1H,H-8),4.56(d,J=8.0Hz,2H,H-8,H-1'),3.85(t,J=13.4Hz,2H,H-6 '),3.64(m,3H,H-3',H-4',H-11),3.49(s,1H,H-2'),3.36(s,1H,H-5'), 2.96(d,J=7.1Hz,1H,H-6),2.79(t,J=9.4Hz,1H,H-5),2.68-2.55(m, 2H,H-3),1.99(d,J=11.8Hz,1H,H-6),1.47-1.32(m,5H,H-10,H-12),1.06 (d,J=6.2Hz,1H,H-13),0.86(d,J=6.1Hz,2H,H-13),0.78(t,J=7.4Hz,2H,H-14),0.63(t,J=7.4Hz,1H,H-14). 13CNMR(101MHz,Chloroform-d) δ205.47(C-4),167.39(C-7"),133.74(C-4"),129.91(C-2",C-6"),129.31(C -1"),128.63(C-3",C-5"),104.19,102.66(C-9),98.72(C-1'),88.01,87.94 (C-1),85.66,85.57(C-2),76.50,76.17(C-11),75.93(C-3'),74.75(C-5') ,73.67(C-2'),69.70(C-4'),63.15(C-7),63.11(C-8),61.68(C-6'),48.97 (C-6),46.99(C-5),29.83,29.33(C-12),28.59(C-3),20.80(C-10),19.74,17.95(C-13),9.43,9.23(C-14).MS-ESI m / z Calcd for C 27 H 36 O 11 Na[M+Na] + 558.57, found 559.15.

[0160] Compound 33, white powder, 17.5 mg, yield 36.8%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0161]

[0162] R f 0.05 (CH2Cl2:CH3OH, 7:1). 11H NMR (400 MHz, Acetone-d6) δ 5.33 (d, J = 16.3 Hz, 1H, H-9), 4.76 (d, J = 9.5 Hz, 1H, H-8), 4.02 (dd, J = 12.5, 5.9 Hz, 1H, H-6'), 3.81 (d, J = 9.3 Hz, 1H, H-11), 3.73 - 3.59 (m, 3H, H-6', H-5', H-4'), 3.46 (t, J = 8.8 Hz, 1H, H-3'), 3.32 (m, 3H, H-2', H-1', H-8), 2.89 (t, J = 11.0 Hz, 1H, H-5), 2.74 (dd, J = 17.7, 3.2 Hz, 1H, H-6), 2.43 (dd, J = 17.4, 4.3 Hz, 2H, H-3), 2.08 (d, J = 3.9 Hz, 1H, H-6), 1.41 (m, 2H, H-12), 1.34 (s, 3H, H-10), 1.05 (dd, J = 21.8, 6.2 Hz, 3H, H-13), 0.83 (q, J = 7.7 Hz, 3H, H-14). 13 13C NMR (101 MHz, Acetone-d6) δ 205.62, 205.44 (C-4), 103.33, 101.47 (C-9), 98.88 (C-1'), 88.20, 87.95 (C-1), 86.89 (C-2), 78.22, 77.50 (C-11), 76.37 (C-3'), 75.06 (C-5'), 74.53 (C-2'), 71.74 (C-4'), 65.32, 65.15 (C-7), 62.96 (C-6'), 60.23, 60.04 (C-8), 59.64 (C-3), 49.68, 49.62 (C-5), 47.34, 47.23 (C-12), 26.81, 26.71 (C-6), 20.87 (C-10), 20.56, 18.80 (C-13), 10.01, 9.64 (C-14). MS-ESI m / z Calcd for C 20 H 32 O 10 Na[M+Na] + 455.47, found 455.65.

[0163] Example XIX

[0164] Paeoniflorin (80 mg, 0.17 mmol) was dissolved in benzyl alcohol (benzyl alcohol, 3 mL) / THF (3 mL), and refluxed at 66°C for 45 min under the catalysis of Sc(CF3SO3)3 (84 mg, 0.17 mmol). The reaction solution was poured into water, extracted with EtOAc 3 times, and washed with saturated NaCl 3 times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated to dryness. After the organic phase was concentrated, a mixture of compound 4-O-benzylpaeoniflorin and compound 37 (85 mg, 87.7%) was obtained. The mixture was added to Ac2O / Py (1:1, 6 mL) and reacted at 0°C for 1 h for hydroxyacetylation. After the reaction solution was diluted with EtOAc, it was washed with 5% H2SO4 solution, and then washed with water and saturated NaHCO3 respectively. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated to dryness. Compounds 34 and 35 were purified and separated by column chromatography.

[0165] Compound 34, white powder, 25.2 mg, yield 22.9%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0166]

[0167] R f 0.40 (petroleum:EtOAc, 1.5:1). 1H NMR(400MHz,Chloroform-d)δ8.04 (d,J=7.0Hz,2H,H-2",H-6"),7.61(t,J=7.4Hz,1H,H-4"),7.49(d, J=7.9Hz,2H,H-3",H-5"),7.34-7.26(m,5H,H-2"',H-3"',H-4"',H-5'",H-6"'),5.50(s,1H,H-9),5.12-4.97(m,3H,H-2',H-3',H-4'),4.75(d,J =7.8Hz,1H,H-1'),4.71(s,2H,H-11),4.61(d,J=12.0Hz,1H,H-8),4.50 (d,J=11.9Hz,1H,H-8),4.18(dd,J=12.2,2.6Hz,1H,H-6'),4.11(dd,J=12.2,5.4Hz,1H,H-6'),3.64-3.58(m,1H,H-5'),2.85(d,J=6.8Hz, 1H,H-5),2.33(dd,J=10.8,6.9Hz,1H,H-6),2.16(d,J=10.6Hz,1H,H-3),2.08-1.97(m,13H,4COCH3,H-3),1.82(d,J=10.6Hz,1H,H-6),1.37 (s,3H,H-10). 13 C NMR(101MHz,Chloroform-d)δ170.56,170.35,169.53, 169.44(4CH3 C O),166.53(C-7"),137.81(C-1"'),133.61(C-4"),129.77(C-2", C-6"),129.67(C-1"),128.80(C-3",C-5"),128.61(C-3"',C-5"'),127.93(C-4"'),127.73(C-2"',C-6"'),107.83(C-4),101.31(C-9),96.49(C-1'), 88.46(C-1),85.77(C-2),73.09(C-3'),71.90(C-5'),71.43(C-2'),70.01(C-7),68.53(C-4'),66.20(C-11),62.12(C-6'),60.22(C-8),41.93(C-3), 40.98(C-5),22.36(C-6),20.87,20.72,20.70×2(4 CH3CO),19.26(C-10). MS-ESI m / z Calcd for C 38 H 42 O 15 Na[M+Na] + 761.70, found 762.19.

[0168] Compound 35, white powder, 55.7 mg, yield 53.4%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0169]

[0170] R f 0.30 (petroleum:EtOAc, 1.5:1). 1 H NMR(400MHz,Chloroform-d)δ7.94 (d,J=7.8Hz,2H,H-2",H-6"),7.58(t,J=7.5Hz,1H,H-4"),7.38(t, J=7.7Hz,2H,H-3",H-5"),7.23(m,5H,H-2"',H-3"',H-4"',H-5'",H-6" '),5.25-5.16(m,2H,H-9,H-2'),5.06(q,J=9.0,8.2Hz,2H,H-3',H-4'), 4.83-4.75(m,2H,H-1',H-8),4.56-4.45(m,3H,H-8,H-11),4.23-4.12(m ,2H,H-6'),3.71-3.64(m,1H,H-5'),3.11(d,J=7.4Hz,1H,H-5),2.72(s, 2H,H-6,H-3),2.10-1.97(m,14H,4COCH3,H-6,H-3),1.44(s,3H,H-10). 13 C NMR(101MHz,Chloroform-d)δ204.87(C-4),170.52,170.36,169.54,169.48 (4CH3 CO),166.50(C-7"),137.04(C-1"'),133.56(C-4"),129.86(C-1",C-2", C-6"),128.66(C-3",C-5"),128.43(C-3"',C-5"'),127.77(C-2"',C-4"',C -6"'),104.13(C-9),96.33(C-1'),88.06(C-1),86.22(C-2),73.01(C-2'), 72.11(C-5'),71.54(C-3'),70.26(C-8),68.44(C-4'),63.14(C-7),62.38(C-11 ),62.12(C-6'),48.97(C-5),46.96(C-3),26.31(C-6),20.83,20.76,20.71×2(4 C H3CO),20.53(C-10).MS-ESI m / z Calcd for C 38 H 42 O 15 Na[M+Na] + 761.70, found 762.07.

[0171] Embodiment 20

[0172] Compound 34 (60 mg, 0.08 mmol) was dissolved in anhydrous CH3OH (3 mL), and Et3N (0.28 mL, 2.03 mmol) was added. After reacting at room temperature for 24 hours, the reaction solution changed from turbid to clear. The reaction solution was then poured into water, extracted with CH2Cl2 three times, and washed with saturated NaCl three times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated. Compound 36 was obtained by column chromatography.

[0173] Compound 36, white powder, 15.3 mg, yield 32.8%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0174]

[0175] R f0.08 (CH2Cl2:CH3OH, 7:1). H NMR (400 MHz, Acetone-d6) δ 7.39 - 7.23 (m, 5H, H-2''', H-3''', H-4''', H-5''', H-6'''), 5.28 (s, 1H, H-9), 4.73 - 4.64 (m, 3H, H-8, H-1'), 4.03 (d, J = 12.3 Hz, 1H, H-11), 3.93 (d, J = 12.3 Hz, 1H, H-11), 3.82 (d, J = 11.7 Hz, 1H, H-6'), 3.63 (dd, J = 12.0, 4.2 Hz, 1H, H-6'), 3.46 (t, J = 8.4 Hz, 1H, H-3'), 3.34 (d, J = 4.7 Hz, 2H, H-4', H-5'), 3.24 (t, J = 9.2 Hz, 1H, H-2'), 2.61 (d, J = 8.6 Hz, 1H, H-6), 2.44 (dd, J = 10.7, 6.9 Hz, 1H, H-5), 2.13 (d, J = 12.2 Hz, 1H, H-3), 1.95 (d, J = 12.2 Hz, 1H, H-3), 1.87 (d, J = 10.7 Hz, 1H, H-6), 1.32 (s, 3H, H-10). 13 C NMR (101 MHz, Acetone-d6) δ 139.66 (C-1'''), 129.03 (C-3''', C-5'''), 128.23 (C-2''', C-6'''), 128.13 (C-4'''), 108.66 (C-4), 102.08 (C-9), 99.47 (C-1'), 88.96 (C-1), 86.21 (C-2), 78.18 (C-3'), 77.44 (C-5'), 74.80 (C-2'), 72.84 (C-7), 71.78 (C-4'), 66.02 (C-11), 62.99 (C-6'), 59.07 (C-8), 42.82 (C-3), 41.07 (C-5), 23.25 (C-6), 19.64 (C-10). MS-ESI m / z Calcd for C 23 H 30 O 10 Na[M+Na] + 489.48, found 490.35.

[0176] Example 21

[0177] Compound 35 (80 mg, 0.11 mmol) was dissolved in anhydrous CH3OH (3 mL), and Et3N (0.37 mL, 2.71 mmol) was added. After reacting at room temperature for 24 hours, the reaction solution changed from turbid to clear. The reaction solution was then poured into water, extracted with CH2Cl2 three times, and washed with saturated NaCl three times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated. Compounds 37 and 38 were obtained by column chromatography.

[0178] Compound 37, white powder, 29.0 mg, yield 46.2%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0179]

[0180] R f 0.35 (CH2Cl2:CH3OH, 7:1). 1 H NMR (400MHz, Chloroform-d) δ7.76 (d, J=7.7Hz, 2H, H-2", H-6"), 7.40 (t, J=7.5Hz, 1H, H-4"), 7.13 (m, 7H, H-3",H-5",H-2"',H-3"',H-4"',H-5"',H-6"'),5.20(s,1H,H-9),4.69( dd,J=12.1,6.8Hz,2H,H-11),4.55(d,J=11.2Hz,2H,H-8,H-1'),4.33(d, J=12.1Hz,1H,H-8),3.83(s,2H,H-6'),3.66(s,2H,H-3',H-4'),3.49(s,1H,H-2'),3.38(s,1H,H-5'),3.00(d,J=6.8Hz,1H,H-6),2.81(s, 1H,H-5),2.72-2.55(q,J=22.3Hz,2H,H-3),2.02(d,J=10.6Hz,1H,H-6),1.41(s,3H,H-10). 13CNMR(101MHz,Chloroform-d)δ205.40(C-4),167.35 (C-7"),137.17(C-1"'),133.62(C-4"),129.84(C-2"',C-6"'),129.16(C -4"'),128.59(C-3"',C-5"'),128.32(C-3",C-5"),127.56(C-1"),127.42 (C-2",6"),104.95(C-9),98.69(C-1'),87.98(C-1),86.33(C-2),76.49(C -2'),75.92(C-5'),73.72(C-3'),70.34(C-8),69.71(C-4'),63.57(C-7), 63.27(C-11),61.59(C-6'),48.90(C-5),47.06(C-3),26.62(C-6),20.72(C-10).MS-ESI m / zCalcd for C 30 H 34 O 11 Na[M+Na] + 593.59, found 593.18.

[0181] Compound 38, white powder, 18.8 mg, yield 36.6%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0182]

[0183] R f 0.08 (CH2Cl2:CH3OH, 7:1). 11H NMR (400 MHz, Acetone-d6) δ 7.51 - 7.37 (m, 5H, H-2''', H-3''', H-4''', H-5''', H-6'''), 5.50 (s, 1H, H-9), 4.64 (d, J = 12.2 Hz, 1H, H-8), 4.20 (d, J = 12.5 Hz, 1H, H-6'), 3.99 (dd, J = 11.7, 2.6 Hz, 1H, H-11), 3.91 (d, J = 12.5 Hz, 1H, H-6'), 3.79 (dd, J = 11.7, 5.6 Hz, 1H, H-11), 3.70 - 3.62 (m, 2H, H-4', H-5'), 3.50 (m, 4H, H-2', H-3', H-8, H-1'), 3.10 (dd, J = 11.1, 7.5 Hz, 1H, H-5), 2.97 (d, J = 18.0 Hz, 1H, H-6), 2.73 (d, J = 7.4 Hz, 1H, H-3), 2.64 (d, J = 18.0 Hz, 1H, H-6), 2.27 (d, J = 11.0 Hz, 1H, H-3), 1.55 (s, 3H, H-10). 13 13C NMR (101 MHz, Acetone-d6) δ 205.58 (C-4), 139.16 (C-1'''), 128.92 (C-3''', C-5'''), 128.25 (C-2''', C-6'''), 128.02 (C-4'''), 103.88 (C-9), 98.94 (C-1'), 88.32 (C-1), 87.42 (C-2), 78.24 (C-2'), 77.53 (C-5'), 74.58 (C-3'), 71.80 (C-8), 70.63 (C-4'), 65.46 (C-7), 63.01 (C-11), 60.18 (C-6'), 49.59 (C-5), 47.29 (C-3), 26.74 (C-6), 20.78 (C-10). MS-ESI m / z Calcd for C 23 H 30 O 10 Na[M+Na] + 489.48, found 489.16.

[0184] Example 22

[0185] Paeoniflorin (80 mg, 0.17 mmol) was dissolved in a mixed solvent of phenethyl alcohol (phenylethanol, 3 mL) and THF (tetrahydrofuran, 3 mL), and refluxed at 66°C for 60 min under the catalysis of Sc(CF3SO3)3 (84 mg, 0.17 mmol). The reaction solution was poured into water, extracted 3 times with EtOAc, and washed 3 times with saturated NaCl. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated to dryness. After the organic phase was concentrated, a mixture of compound 41 and compound 43 (83 mg, 83.5%) was obtained. Then, the mixture was added to Ac2O / Py (1:1, 6 mL) and reacted at 0°C for 1 h for hydroxyacetylation. After diluting the reaction solution with EtOAc, it was washed with 5% H2SO4 solution, and then washed with water and saturated NaHCO3 respectively. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated to dryness. Compounds 39 and 40 were purified and separated by column chromatography.

[0186] Compound 39, white powder, 32.8 mg, yield 30.7%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0187]

[0188] R f 0.42 (petroleum:EtOAc, 1.5:1). 1H NMR(400MHz,Chloroform-d)δ8.02 (d,J=8.5Hz,2H,H-2",H-6"),7.60(t,J=7.5Hz,1H,H-4"),7.46(t, J=7.8Hz,2H,H-3",H-5"),7.26-7.16(m,5H,H-2"',H-3"',H-4"',H-5'",H-6"'),5.43(s,1H,H-9),5.11-4.96(m,3H,H-2',H-3',H-4'),4.73(d,J =7.8Hz,1H,H-1'),4.58(d,J=12.0Hz,1H,H-8),4.47(d,J=12.0Hz, 1H,H-8),4.16(d,J=2.6Hz,1H,H-6'),4.11(dd,J=12.2,5.3Hz,1H,H-6'),3.83(t,J=6.8Hz,2H,H-11),3.63-3.57(m,1H,H-5'),2.88(t,J =7.7Hz,2H,H-12),2.72(d,J=8.6Hz,1H,H-5),2.28(dd,J=10.8,7.0 Hz,1H,H-6),2.06,2.03,2.02,1.98(m,13H,4COCH3,H-3),1.93(d,J=12.5 Hz,1H,H-3),1.75(d,J=10.7Hz,1H,H-6),1.33(s,3H,H-10). 13 C NMR(101 MHz,Chloroform-d)δ170.54,170.33,169.51,169.41(4CH3 CO),166.49(C-7"), 138.50(C-1"'),133.57(C-4"),129.74(C-2",C-6"),129.66(C-1"),129.06( C-3",C-5"),128.76(C-3"',C-5"'),128.48(C-2"',C-6"'),126.45(C-4"'), 107.67(C-4),101.21(C-9),96.45(C-1'),88.44(C-1),85.65(C-2),73.07( C-3'),71.87(C-5'),71.41(C-2'),69.87(C-7),68.52(C-4'),64.97(C-11), 62.10(C-6'),60.22(C-8),41.66(C-3),40.75(C-5),36.58(C-12),22.31(C-6),20.85,20.70,20.68×2(4 C H3CO),19.21(C-10).MS-ESI m / z Calcd for C 39 H 44 O 15 Na[M+Na] + 775.77, found 775.16.

[0189] Compound 40, white powder, 50.8 mg, yield 47.6%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0190]

[0191] R f 0.34 (petroleum:EtOAc, 1.5:1). 1H NMR(400MHz,Chloroform-d)δ7.96 (d,J=6.9Hz,2H,H-2",H-6"),7.62-7.55(m,1H,H-4"),7.43(t,J=7.8 Hz,2H,H-3",H-5"),7.25-7.18(m,2H,H-2"',H-3"'),7.18-7.10(m,3H,H-4"',H-5'",H-6"'),5.16(t,J=9.4Hz,1H,H-2'),5.10(s,1H,H-9),5.07-4.99 (m,2H,H-3',H-4'),4.77(d,J=7.8Hz,1H,H-1'),4.53-4.44(m,2H,H-8), 4.19(dd,J=12.2,2.6Hz,1H,H-6'),4.12(dd,J=12.3,5.5Hz,1H,H-6'),3.89(t,J=7.2Hz,1H,H-11),3.67-3.57(m,2H,H-11,H-5'),3.06(d,J =7.4Hz,1H,H-5),2.78(t,J=7.4Hz,2H,H-12),2.71(dd,J=10.8,7.5 Hz,1H,H-6),2.63(d,J=14.7Hz,1H,H-3),2.05,2.02,1.99(m,14H,4COCH3, H-6,H-3),1.38(s,3H,H-10). 13 C NMR(101MHz,Chloroform-d)δ204.94(C-4), 170.49,170.33,169.52,169.44(4CH3 C O),166.47(C-7"),138.50(C-1"'), 133.60(C-4"),129.78(C-2",C-6"),129.49(C-1"),129.03(C-3",C-5"),128.75(C-3"',C-5"'),128.43(C-2"',C-6"'),126.36(C-4"'),104.77(C-9),96.32(C-1'),87.96(C-1),86.02(C-2),73.01(C-2'),72.08(C-5'),71.53(C-3'),69.58(C-8),68.43(C-4'),63.07(C-7),62.34(C-11),62.10(C-6'), 48.86(C-5),46.98(C-3),35.89(C-12),26.34(C-6),20.82,20.72,20.69×2 (4C H3CO),20.48(C-10).MS-ESI m / zCalcd for C 39 H 44 O 15 Na[M+Na] + 775.77, found 775.17.

[0192] Embodiment 23

[0193] Compound 39 (67 mg, 0.09 mmol) was dissolved in anhydrous CH3OH (3 mL), and Et3N (0.30 mL, 2.23 mmol) was added. After reacting at room temperature for 24 hours, the reaction solution changed from turbid to clear. The reaction solution was then poured into water, extracted with CH2Cl2 three times, and washed with saturated NaCl three times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated. Compounds 41 and 42 were obtained by column chromatography.

[0194] Compound 41, white powder, 23.6 mg, yield 44.9%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0195]

[0196] R f 0.36 (CH2Cl2:CH3OH, 7:1). 1 H NMR(400MHz,Chloroform-d)δ7.89(d, J=7.7Hz,2H,H-2",H-6"),7.44(t,J=7.5Hz,1H,H-4"),7.29(d,J=7.7Hz,2H,H-3",H-5"),7.25-7.11(m,5 H,H-2"',H-3"',H-4"',H-5"',H-6"'),5.46(s,1H,H-9),4.63(q,J=12.1Hz,2H,H-8,H-1'),4.48(d,J=7.3 Hz,1H,H-8),3.83-3.71(m,4H,H-6',H-11),3.57(s,2H,H-3',H-4'),3. 39(s,1H,H-2'),3.28(s,1H,H-5'),2.84(t,J=7.4Hz,2H,H-12),2.64(d, J=6.5Hz,1H,H-6),2.38-2.30(t,J=11.5Hz 1H,H-5),1.92(s,2H,H-3), 1.75(d,J=10.6Hz,1H,H-6),1.31(s,3H,H-10). 13C NMR(101MHz, Chloroform-d)δ167.10(C-7"),138.50(C-1"'),133.48(C-4"),129.81(C-2 ",C-6"),129.58(C-1"),129.05(C-3",C-5"),128.64(C-3"',C-5"'),128.49 (C-2"',C-6"'),126.43(C-4"'),107.75(C-4),101.28(C-9),98.92(C-1') ,88.48(C-1),85.71(C-2),76.41(C-3'),75.72(C-5'),73.52(C-2'),70.08 (C-7),69.52(C-4'),64.80(C-11),61.65(C-6'),60.84(C-8),41.79(C-3),40.24(C-5),36.57(C-12),22.76(C-6),19.51(C-10).MS-ESI m / z Calcd for C 31 H 36 O 11 Na[M+Na] + 607.62,found607.20.

[0197] Compound 42, white powder, 14.7 mg, yield 34.0%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0198]

[0199] R f 0.07 (CH2Cl2:CH3OH, 7:1). 11H NMR (400 MHz, Acetone-d6) δ 7.30 - 7.16 (m, 5H, H-2''', H-3''', H-4''', H-5''', H-6'''), 5.22 (s, 1H, H-9), 4.65 (d, J = 7.7 Hz, 1H, H-8), 3.99 (dd, J = 12.4, 4.0 Hz, 1H, H-11), 3.89 (dd, J = 12.3, 6.4 Hz, 1H, H-11), 3.84 - 3.76 (m, 3H, H-8, H-1', H-6'), 3.62 (d, J = 10.9 Hz, 1H, H-6'), 3.46 - 3.42 (m, 1H, H-3'), 3.35 - 3.30 (m, 2H, H-4', H-5'), 3.23 (t, J = 7.4 Hz, 1H, H-2'), 2.83 (t, J = 7.2 Hz, 2H, H-12), 2.50 (d, J = 8.7 Hz, 1H, H-6), 2.39 (dd, J = 10.7, 6.9 Hz, 1H, H-5), 2.01 (d, J = 12.2 Hz, 1H, H-3), 1.85 (dd, J = 12.3, 1.9 Hz, 1H, H-3), 1.79 (d, J = 10.6 Hz, 1H, H-6), 1.28 (s, 3H, H-10). 13 13C NMR (101 MHz, Acetone-d6) δ 139.88 (C-1'''), 129.79 (C-3''', C-5'''), 129.07 (C-2''', C-6'''), 126.94 (C-4'''), 108.45 (C-4), 101.98 (C-9), 99.44 (C-1'), 88.90 (C-1), 86.09 (C-2), 78.16 (C-3'), 77.43 (C-5'), 74.41 (C-2'), 72.69 (C-7), 71.76 (C-4'), 64.97 (C-11), 62.98 (C-6'), 58.46 (C-8), 42.56 (C-3), 40.93 (C-5), 37.17 (C-12), 23.18 (C-6), 19.61 (C-10). MS-ESI m / z Calcd for C 24 H 32 O 10 Na[M+Na] + 503.51, found 504.12.

[0200] Example 24

[0201] Compound 40 (80 mg, 0.11 mmol) was dissolved in anhydrous CH3OH (3 mL), and Et3N (0.37 mL, 2.65 mmol) was added. After reacting at room temperature for 24 hours, the reaction solution changed from turbid to clear. The reaction solution was then poured into water, extracted with CH2Cl2 three times, and washed with saturated NaCl three times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated. Compounds 43 and 44 were obtained by column chromatography.

[0202] Compound 43, white powder, 30.5 mg, yield 47.4%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0203]

[0204] R f 0.37 (CH2Cl2:CH3OH, 7:1). 1 H NMR (400MHz, Chloroform-d) δ7.82 (d, J=7.8Hz, 2H, H-2", H-6"), 7.45 (t, J=7.5Hz, 1H, H-4"), 7.27 (d, J= 15.3Hz,2H,H-3",H-5"),7.20-7.02(m,5H,H-2"',H-3"',H-4"',H-5"',H- 6"'),5.10(s,1H,H-9),4.71(d,J=11.7Hz,1H,H-8),4.52(d,J=11.0Hz,2H, H-8,H-1'),3.86-3.75(m,3H,H-6',H-11),3.65(s,2H,H-3',H-4'),3.50-3.43 (m,2H,H-2',H-11),3.35(s,1H,H-5'),2.97(d,J=6.9Hz,1H,H-6),2.78(t,J=9.0Hz,1H,H-5),2.69(t,J=7.4Hz,2H H-12), 2.66-2.46 (q, J=27.9Hz, 2H, H-3), 1.97 (d, J=10.9Hz, 1H, H-6), 1.36 (s, 3H, H-10). 13C NMR(101MHz,Chloroform-d)δ205.36(C-4),167.30(C-7"),138.48(C-1"'),133.67(C-4"),129.78(C-2",C-6"),129.29(C-1"),129.00(C-3",C-5"), 128.70(C-3"',C-5"'),128.41(C-2"',C-6"'),126.34(C-4"'),105.11(C-9),98.71(C-1'),88.00(C-1),86.00(C- 2),76.51(C-2'),75.91(C-5'),73.65(C-3'),69.58(C-8),69.47(C-4'),63.45(C-7),63.13(C-11),61.58(C-6'), 48.80(C-5),47.01(C-3),46.12,35.84(C-12),26.60(C-6),20.68(C-10).MS-ESI m / z Calcd for C 31 H 36 O 11 Na[M+Na] + 607.62, found 607.17.

[0205] Compound 44, white powder, 17.4 mg, yield 32.9%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0206]

[0207] R f 0.06 (CH2Cl2:CH3OH, 7:1). 11H NMR (400 MHz, Acetone-d6) δ 7.36 - 7.12 (m, 5H, H-2''', H-3''', H-4''', H-5''', H-6'''), 5.22 (s, 1H, H-9), 4.78 (d, J = 7.7 Hz, 1H, H-8), 4.01 (d, J = 12.5 Hz, 1H, H-6'), 3.89 - 3.81 (m, 2H, H-11, H-6'), 3.71 - 3.57 (m, 3H, H-11, H-4', H-5'), 3.50 - 3.46 (m, 1H, H-3'), 3.40 - 3.27 (m, 3H, H-8, H-1', H-2'), 2.92 (dd, J = 11.1, 7.6 Hz, 1H, H-5), 2.78 (q, J = 7.4 Hz, 3H, H-6, H-12), 2.53 (d, J = 7.5 Hz, 1H, H-3), 2.42 (d, J = 17.9 Hz, 1H, H-3), 2.09 (d, J = 9.6 Hz, 1H, H-6), 1.36 (s, 3H, H-10). 13 13C NMR (101 MHz, Acetone-d6) δ 205.45 (C-4), 140.02 (C-1'''), 129.89 (C-3''', C-5'''), 129.01 (C-2''', C-6'''), 126.86 (C-4'''), 103.96 (C-9), 98.89 (C-1'), 88.17 (C-1), 87.16 (C-2), 78.27 (C-2'), 77.53 (C-5'), 74.56 (C-3'), 71.78 (C-8), 69.85 (C-4'), 65.30 (C-7), 63.00 (C-11), 60.16 (C-6'), 49.46 (C-5), 47.30 (C-3), 36.48 (C-12), 26.65 (C-6), 20.75 (C-10). MS-ESI m / z Calcd for C 24 H 32 O 10 Na[M+Na] + 503.51, found 503.48.

[0208] Example 25

[0209] Paeoniflorin (150 mg, 0.31 mmol) was dissolved in ter-butanol (tert-butyl alcohol, 8 mL), and refluxed at 83 ° C for 10 h under the catalysis of Sc(CF3SO3)3 (154 mg, 0.31 mmol). The reaction solution was poured into water, extracted with EtOAc 3 times, and washed with saturated NaCl 3 times. The organic phase was dried over anhydrous Na2SO4, concentrated, and evaporated to dryness. Compounds 45 and 46 were purified and separated by column chromatography.

[0210] Compound 45, white powder, 24.1 mg, yield 14.5%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0211]

[0212] R f 0.46 (CH2Cl2:CH3OH, 7:1). 1 H NMR (400MHz, Chloroform-d) δ7.97 (d, J=7.1Hz, 2H, H-2", H-6"), 7.51 (t, J=7.6Hz, 1H, H-4"), 7.37 (t, J= 7.7Hz,2H,H-3",H-5"),5.51(s,1H,H-9),4.73(d,J=12.0Hz,1H,H-8),4.61(d,J=12.3Hz,1H,H-8),4.43(d,J=7.5Hz,1H,H-1'),3.62-3.31 (m,6H,H-6',H-5',H-4',H-3',H-2'),2.59(d,J=6.3Hz,1H,H-6),2.38-2.31(m,1H,H-5),2.09(d,J=12.4Hz,1H,H-3),1.88(dd,J=22.4,11.5Hz, 2H,H-3,H-6),1.33(s,3H,H-12),1.25(s,3H,H-14),1.14(d,J=9.9Hz,6H,H-10,H-13). 13C NMR(101MHz,Chloroform-d)δ167.14(C-7"),133.60 (C-4"),129.90(C-2",C-6"),129.54(C-1"),128.70(C-3",C-5"),105.27(C- 4),100.90(C-9),98.52(C-1'),88.38(C-1),86.00(C-2),76.45(C-3'),74.11 (C-5'),73.65(C-2'),73.39(C-4'),72.33(C-8),70.43(C-11),62.85(C-7),60.45(C-6' ),42.95(C-6),29.71(C-12,C-3),27.43(C-10,C-13),22.70(C-5),19.27(C-14).MS-ESI m / z Calcd for C 27 H 36 O 11 Na[M+Na] + 559.57, found 559.80.

[0213] Compound 46, white powder, 21.3 mg, yield 12.8%; this compound is a newly synthesized and first disclosed compound. Its structural formula and test data are as follows:

[0214]

[0215] R f 0.26 (CH2Cl2:CH3OH, 7:1). 1H NMR (400MHz, Chloroform-d) δ7.93 (d, J=7.3Hz, 2H, H-2", H-6"), 7.51 (t, J=7.4Hz, 1H, H-4"), 7.36 (t, J= 7.7Hz,2H,H-3",H-5"),5.39(s,1H,H-9),4.80(d,J=11.8Hz,1H,H-8),4 .59-4.49(m,2H,H-8,H-1'),3.84(s,2H,H-6'),3.65(s,2H,H-3',H-4'), 3.48(s,1H,H-2'),3.36(s,1H,H-5'),2.95(d,J=7.1Hz,1H,H-6),2.81-2.74 (m,1H,H-5),2.63(s,2H,H-3),1.98(d,J=10.9Hz,1H,H-6),1.38(s, 3H,H-14),1.25(s,2H,H-12),1.07(s,7H,H-10,H-13,H-12). 13 C NMR(101 MHz,Chloroform-d)δ205.88(C-4),167.23(C-7"),133.71(C-4"),129.87(C -2",C-6"),129.36(C-1"),128.67(C-3",C-5"),99.98(C-9),98.67(C-1'), 87.58(C-1),85.43(C-2),76.50(C-2'),75.91(C-5'),73.72(C-3'),69.70 (C-4'),63.50(C-8),63.44(C-7),61.63(C-6'),49.11(C-3),46.86(C-6), 29.84(C-12),28.77(C-10,C-13),28.56(C-5),20.92(C-14).MS-ESI m / zCalcd for C 27 H 36 O 11 Na[M+Na] + 559.57, found 559.60.

[0216] The embodiments described above are only descriptions of the preferred modes of the present invention and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various deformations, modifications, and substitutions made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. A method for preparing a paeoniflorin derivative, characterized in that: Using Sc(CF3SO3)3 as a catalyst, alcohols as a reaction solvent, and paeoniflorin as a raw material, alkylating the C-4 and C-9 positions of paeoniflorin through dehydration reaction and acetal reaction to prepare paeoniflorin derivatives; The alcohol is any one of methanol, ethanol, benzyl alcohol or a mixture of several thereof. When the alcohol is benzyl alcohol, benzyl alcohol and tetrahydrofuran are used as the reaction solvent in a volume ratio of 1:

1. The molar ratio of paeoniflorin to Sc(CF3SO3)3 is 1:1; and the reaction temperature is the boiling point of the reaction solvent.

2. The method for preparing paeoniflorin derivatives according to claim 1, characterized in that: The reaction equation is: R is one of methyl, ethyl and benzyl.

3. The method for preparing paeoniflorin derivatives according to claim 1, characterized in that: When the obtained paeoniflorin derivative is a mixture of multiple paeoniflorin derivatives, the method for separating the paeoniflorin derivative mixture is: subjecting the mixture to acetylation of the hydroxyl groups on the glucose group, separating the obtained acetylated products from each other, and then subjecting each separated acetylated product to deacetylation.

4. The method for preparing paeoniflorin derivatives according to claim 3, characterized in that: The conditions for the acetylation reaction of the hydroxyl group on the glucose group are: reacting in a mixed solvent of pyridine:acetic anhydride at a volume ratio of 1:1, and reacting at 0° C. for 1 hour.

5. The method for preparing paeoniflorin derivatives according to claim 3, characterized in that: The deacetylation reaction conditions are: adding triethylamine to the methanol solution for reaction, and reacting at room temperature for 24 hours.

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