CN103694282A - Synthetic method of Tenuifoliside B - Google Patents
Synthetic method of Tenuifoliside B Download PDFInfo
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- CN103694282A CN103694282A CN201310614825.8A CN201310614825A CN103694282A CN 103694282 A CN103694282 A CN 103694282A CN 201310614825 A CN201310614825 A CN 201310614825A CN 103694282 A CN103694282 A CN 103694282A
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- acetoxy
- dimethoxy
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Abstract
The invention provides a synthetic method of Tenuifoliside B. Sucrose, syringaldehyde and p-hydroxybenzoic acid are used as the starting materials, and subjected to 6 steps of chemical conversion reactions to realize total synthesis of Tenuifoliside B for the first time. The raw materials of sucrose, syringaldehyde and p-hydroxybenzoic acid employed by the invention are convenient, easily available and at controllable low cost; each step of chemical reaction has mild reaction conditions and is easy to implement and operate in the practical application; each step of chemical reaction has high reaction conversion rate, especially the first three reaction steps have mild reaction conditions, simple operations, high yield, small amount of by-products and total yield at about 22.3%; and the Tenuifoliside B can be directly used for subsequent steps of the synthesis reaction without fine column chromatography purification.
Description
Technical field
The invention belongs to the field of chemical synthesis, relate to the chemical synthesis process of the natural product Tenuifoliside B with cerebral protection.
Background technology
Tenuifoliside B(compound
1) be from Chinese medicine polygala root (
polygala tenuifoliawilld.) sugar esters compounds (Yukinobu Ikeya, Ko Sugama, Minoru Okada, Hiroshi Mitsuhashi. that in, separation obtains
chem. Pharm Bull., 1991,39 (10), 2600-2605.), be natural product.The chemical structural formula of this natural product (Tenuifoliside B) is as follows:
The pharmacological results shows Tenuifoliside B(3-10 mg/kg,
p. o.) the Rats With Memory defect tool of Scopolamine and sodium cyanide induction is significantly improved, with the activity of positive drug tacrine similar (Yukinobu I, Shigefumi T, Mitsuo T, Humito K, Kouin T, Takuji Y and Masaki A.
biol. and Pharm. Bulletin., 2004,27,1081-1085.), can be used for preparing anti-senile dementia product, particularly medicine.
The main source of Tenuifoliside B is that plant extract is separated at present.Due to the content of Tenuifoliside B in polygala root lower (being about 0.1%), impurity disturbs many, separation difficulty, and yield is very low, is difficult to meet scientific research, Production requirement.As within 2008, slaughter roc fly etc. report from 9 Kg ovum leaf polygala roots only separation obtain 18 mg Tenuifoliside B.At present, the report that also there is no Tenuifolidise B chemosynthesis.
Summary of the invention
In order to solve the deficiencies in the prior art, the invention provides that a kind of to take sucrose, syringic aldehyde, P-hydroxybenzoic acid be the preparation method of the synthetic Tenuifoliside B of starting raw material, effectively solved the problem that prior art exists.
Preparation method provided by the invention realizes by following steps:
(1) respectively with syringic aldehyde (
2), P-hydroxybenzoic acid (
3) be raw material, through ethanoyl protection, make 4-acetoxy-3,5-dimethoxy benzaldehyde (
5) and 4-ABA (
6); Solvent is pyridine, and reaction reagent is diacetyl oxide, and temperature of reaction is solvent refluxing, and the reaction times is 2 hours.
(2) 4-acetoxy-3,5-dimethoxy benzaldehyde (
5) through Knoevenagel condensation reaction, make 4-acetoxy-3,5-dimethoxy-cinnamic acid (
7); Reaction solvent is pyridine, and reaction reagent is propanedioic acid, and catalyzer is piperidines, and holding aqua under the arm is benzene, and temperature of reaction is solvent refluxing, and the reaction times is 3 hours.
(3) 4-acetoxy-3,5-dimethoxy-cinnamic acid (
7) dewater and make 4-acetoxy-3,5-dimethoxy-cinnamic acid acid anhydride (
8); Reaction solvent is anhydrous ethyl acetate, and reaction reagent is triethylamine and triphosgene, and 0 ℃ is reacted 10 minutes, room temperature reaction 25 minutes.
(4) 4-acetoxy-3,5-dimethoxy-cinnamic acid acid anhydride (
8) and sucrose (
4) carry out esterification, obtain 3 '-
o-(4-acetoxy-3,5-dimethoxy-cinnamoyl) sucrose (
9); Reaction solvent is DMF, reaction reagent 4-acetoxy-3, and 5-dimethoxy-cinnamic acid acid anhydride, catalyzer is cobalt chloride and triethylamine, and temperature of reaction is room temperature, and the reaction times is 1 hour.Wherein the mol ratio of sucrose and acid anhydrides is 1:1.3, and the mol ratio of sucrose and sodium hydride is 1:8, and the mol ratio of sucrose and cobalt chloride is 1:0.5.
(5) 3 '-
o-(4-acetoxy-3,5-dimethoxy-cinnamoyl) sucrose (
9) and 4-ABA (
6) carry out light and prolong reaction, obtain 3 '-
o-(4-acetoxy-3,5-dimethoxy-cinnamoyl)-6-
o-(4-acetoxy benzoyl) sucrose (
10); Reaction solvent DMF, reaction reagent is 4-ABA, and catalyzer is triphenyl phosphorus and diisopropyl azodiformate, and temperature of reaction is 75 ℃, and the reaction times is 0.5 hour.Wherein 3 '-
othe mol ratio of-(4-acetoxy-3,5-dimethoxy-cinnamoyl) sucrose and 4-ABA is 1:2.5 ~ 3.0, preferably 1:2.5.3 '-
othe mol ratio of-(4-acetoxy-3,5-dimethoxy-cinnamoyl) sucrose and triphenyl phosphorus/diisopropyl azodiformate is 1:2.7 ~ 3.2, preferably 1:2.7.
(6) 3 '-
o-(4-acetoxy-3,5-dimethoxy-cinnamoyl)-6-
o-(4-acetoxy benzoyl) sucrose (
10) de-acetyl protection base generation target product Tenuifoliside B(
1); Reaction solvent is 80% methyl alcohol, and catalyzer is ammonium acetate, and temperature of reaction is room temperature, and the reaction times is 24 hours.3 '-O-(4-acetoxy-3 wherein, 5-dimethoxy-cinnamoyl)-6-O-(4-acetoxy benzoyl) mol ratio of sucrose and Dibutyltin oxide is 1:8.
Synthetic route of the present invention is as follows:
The complete synthesis preparation method of Tenuifoliside B of the present invention chemistry, take sucrose, syringic aldehyde, P-hydroxybenzoic acid is starting raw material, chemical through 6 steps altogether, complete synthesis first Tenuifoliside B.Compared with prior art, it has the following advantages:
A) synthetic desired raw material sucrose, syringic aldehyde, P-hydroxybenzoic acid etc. are cheaply easy to get, and cost is cheaply controlled;
B) respectively walk the reaction conditions gentleness of chemical conversion reaction, in actual applications easy implementation and operation;
C) respectively walk reaction conversion ratio higher, especially before three-step reaction, the high by product of yield is few, and just can be directly used in subsequent step building-up reactions without meticulous column chromatography purification.
Embodiment
In order further to illustrate the present invention, provide some embodiment below, these embodiment are illustrative completely, they are only used for the present invention to specifically describe, and not should be understood to limitation of the present invention.
Embodiment 1
4-acetoxy-3,5-dimethoxy-cinnamic acid (
7) preparation:
By syringic aldehyde (
2) 60.06 g(330 mmol) be dissolved in 360 mL pyridines, add diacetyl oxide 36.72 g(360 mmol), reflux 2 hours, be cooled to room temperature, directly drop into next step reaction, add benzene 500 mL, propanedioic acid 52.00 g(500 mmol), piperidines 5 mL, load onto the reflux with water trap, oil bath, stirring and dissolving, refluxes 3 hours.React complete, be cooled to room temperature, add 1000 mL saturated sodium bicarbonate solutions, stir, isolate water layer, by 6 mol/L hcl acidifyings to pH value, be about 5, filter, filter cake rinses with 500 ml water, dry, obtain white solid 4-acetoxy-3,5-dimethoxy-cinnamic acid (
7) 56.18 g, yield 64%.4-acetoxy-3, the fusing point of 5-dimethoxy-cinnamic acid, spectroscopic data, high resolution mass spectrum data: fusing point 202-204 ° C;
=+0.2(c=1.01, MeOH);
1h NMR(500 MHz, CD
3cOCD
3): δ=7.63(d,
j=16 Hz, 1 H), 7.08(s, 2 H), 6.56(d,
j=16 Hz, 1 H), 3.87(s, 6H) and, 2.24(s, 3 H) ppm;
13c NMR(125 MHz, CD
3cOCD
3): δ=169.1,168.5,154.2(2 C), 14,6.0,134.4,132.0,106.5(2 C) and, 57. 3(2 C), 20.9 ppm; HRMS(ESI): 289.0683(calcd. for C
13h
14o
6na [M+Na]
+289.0688).
Embodiment 2
4-ABA (
6) preparation:
By P-hydroxybenzoic acid (
3) 4.55 g(33 mmol) be dissolved in 30 mL pyridines, add diacetyl oxide 3.67 g(36 mmol), reflux 2 hours.React complete, be cooled to room temperature, add 100 mL saturated sodium bicarbonate solutions, stir, isolate water layer, with 6 mol/L hcl acidifyings to pH value, be about 2, filtration, filter cake rinses with 50 ml water, oven dry, obtain white solid 4-globentyl (
6) 5.50 g, yield is 93%.The fusing point of 4-ABA, spectroscopic data, high resolution mass spectrum data: fusing point 191-193 ° C;
1h NMR(500 MHz, CD
3oD): δ=8.06(m,
j=8.5,2.5 Hz, 2 H), 7.21(m,
j=8.5,2.5 Hz, 2 H), 2.29(s, 3 H) and ppm;
13c NMR(125 MHz, CD
3oD): δ=170.7,169.1,156.1,132.4(2 C), 129.6,123.0(2 C), 21.0 ppm; HRMS(ESI): 181.0498(calcd. for C
9h
9o
4[M+H]
+181.0501).
Embodiment 3
4-acetoxy-3,5-dimethoxy-cinnamic acid acid anhydride (
8):
By 4-acetoxy-3,5-dimethoxy-cinnamic acid (
7) 31.92 g(120 mmol) be dissolved in 4000 mL anhydrous ethyl acetates, add anhydrous triethylamine 16.5 mL(120 mmol), ice bath is cooling, under stirring in 0 ℃ of disposable triphosgene 5.94 g(20 mmol that add), react 10 minutes; In room temperature reaction 20 minutes.Filter, anhydrous ethyl acetate for filter cake (1000 mL) washing, merging filtrate and washing lotion, steaming desolventizes, and dries, and obtains white solid 4-acetoxy-3,5-dimethoxy-cinnamic acid acid anhydride (
8), next step reaction of not purified direct input, yield is about 82%.
Embodiment 4
3 '-
o-(4-acetoxy-3,5-dimethoxy-cinnamoyl) sucrose (
9):
By sucrose (
4) 2.05 g(6 mmol) be dissolved in 100 mLN, in dinethylformamide, in 60 ° of C, stir it is dissolved completely, let cool, add triethylamine 6.7 mL(48 mmol) and cobalt chloride 0.71 g(3 mmol), react 30 min, add 4-acetoxy-3,5-dimethoxy-cinnamic acid acid anhydride crude product (
8) 6.00 g(are containing acid anhydrides approximately 7.8 mmol), in room temperature reaction 1 hour.Remove DMF under reduced pressure, resistates is through reversed-phase column chromatography (acetonitrile/water/Glacial acetic acid volume ratio: 1/4/0.004) separated white solid 2.83 g that obtain, yield is 80%.3 '-
o-(4-acetoxy-3,5-dimethoxy-cinnamoyl) sucrose (
9) fusing point, specific optical rotation, spectroscopic data, high resolution mass spectrum data: fusing point 127-129 ° C;
=+10.5(c=1.00, MeOH);
1h NMR(500 MHz, CD
3oD): δ=7.76(d,
j=16 Hz, 1 H), 7.02(s, 2 H), 6.62(d,
j=16 Hz, 1 H), 5.49(d,
j=7.5 Hz, 1 H), 5.44(d,
j=3.5 Hz, 1 H), 4.39(t,
j=7.5 Hz, 1 H), 3.94(m, 2 H) and, 3.86(s, 6 H), 3.77(dd,
j=12,4.6 Hz, 1 H), 3.66(d,
j=12 Hz, 1 H), 3.59(d,
j=12 Hz, 1 H), 3.44(dd,
j=3.5,10 Hz, 1 H), 3.40(t,
j=9.5 Hz, 1 H), 2.26(s, 3 H) and ppm;
13c NMR(125 MHz, CD
3oD): δ=170.4,167.7,154.0(2 C), 147.0,134.3,131.9,119.1,106.3(2 C), 104.9(2 C), 93.5,84.4,80.0,75.1,74.8,74.0,73.2,71.4,65.5,63.0,62.5,57.0(2 C), 20.32 ppm; HRMS(ESI): 613.1746(calcd. for C
25h
34o
16na [M+Na]
+613.1745).
Embodiment 5
3 '-
o-(4-acetoxy-3,5-dimethoxy-cinnamoyl)-6-
o-(4-ABA) sucrose (
10):
By 3 '-
o-(4-acetoxy-3,5-dimethoxy-cinnamoyl) sucrose (
9) solution 1.18 g(2 mmol) be dissolved in 20 mLN, in dinethylformamide, add triphenyl phosphorus 1.42(5.4 mmol), 4-ABA (
6) 0.90 g(5.0 mmol) and DMF 6 mL, add diisopropyl azodiformate 2.09 g(5.4 mmol), 75 ℃ are reacted 1 hour.Remove DMF under reduced pressure, resistates is through reversed-phase column chromatography (methanol/water/Glacial acetic acid volume ratio: 1/1/0.001) separation obtains white solid 0.80 g, and yield is 53%.3 '-
o-(4-acetoxy-3,5-dimethoxy-cinnamoyl)-6-
o-(4-ABA) sucrose (
10) fusing point, specific optical rotation, spectroscopic data, high resolution mass spectrum data: fusing point 132-134 ° C;
=-12.5(c=0.97, MeOH);
1h NMR(500 MHz, CD
3oD): δ=8.08(dd,
j=9,2 Hz, 2 H), 7.74(d,
j=16 Hz, 1 H), 7.21(dd,
j=9,2 Hz, 2 H), 6.99(s, 2 H), 6.60(d,
j=16 Hz, 1 H), 5.50(d,
j=4 Hz, 1 H), 5.50(d,
j=7.5 Hz, 1 H), 4.73(dd,
j=12 2 Hz, 1 H), 4.46(dt,
j=12,5 Hz, 1 H), 4.27(ddd,
j=10,5,2 Hz, 1 H), 3.93(m, 1 H) and, 3.84(s, 6 H), 3.81(m, 1 H) and, 3.70(m, 2 H), 3.65(d, J=12 Hz, 1 H), 3.60(d,
j=12 Hz, 1 H), 3.48(dd,
j=10,3.5 Hz, 1 H), 3.46(t,
j=10 Hz, 1 H), 3.31(m, 2 H) and ppm;
13c NMR(125 MHz, CD
3oD): δ=170.7,170.7,167.7,167.4,156.3,154.0(2 C), 147.0,134.2,132.4(2 C), 131.9,128.8,123.2(2 C), 119.0,106.3(2 C), 105.0,93.3,84.3,79.9,75.0,74.2,73,2,72.6,71.75,65.8,65.7,63.5,57.0(2 C), 21.0,20.3 ppm; HRMS(ESI): 775.2061(calcd. for C
34h
40o
19na [M+Na]
+775.2061).
Embodiment 6
Tenuifoliside?B(
1):
By 3 '-
o-(4-acetoxy-3,5-dimethoxy-cinnamoyl)-6-
o-(4-ABA) sucrose (
10) 0.75 g(1 mmol) be dissolved in 10 mL80% methyl alcohol, add ammonium acetate 0.62 mg(8 mmol), stirring at room 24 hours.Remove solvent under reduced pressure, resistates is through reversed-phase column chromatography (methanol/water/Glacial acetic acid volume ratio: 3/7/0.007) separation obtains yellow look solid 0.60 g, and yield is 90%.Tenuifoliside B(
1) fusing point, specific optical rotation, spectroscopic data, high resolution mass spectrum data: fusing point 144-146 ° C;
=-20.7(c=1.03, MeOH);
1h NMR(500 MHz, CD
3oD): δ=7.91(dd,
j=9,2 Hz, 2 H), 7.70(d,
j=16 Hz, 1 H), 6.93(s, 2 H), 6.92(dd,
j=9,2 Hz, 2 H), 6.45(d,
j=16 Hz, 1 H), 5.50(d,
j=4 Hz, 1 H), 5.48(d,
j=8 Hz, 1 H), 4.66(dd,
j=12 2 Hz, 1 H), 4.44(dd,
j=12,5 Hz, 1 H), 4.37(t,
j=8 Hz, 1 H), 4.24(ddd, 10,5,2 Hz, 1 H) and, 3.93(m, 1 H), 3.87(s, 6 H), 3.81(dd,
j=12.5,6.5 Hz, 1 H), 3.71(m, 2 H), 3.66(d,
j=12 Hz, 1 H), 3.60(d,
j=12 Hz, 1 H), 3.48(dd,
j=10,3.5 Hz, 1 H), 3.46(t,
j=10 Hz, 1 H), 3.31(m, 2 H) and ppm;
13c NMR(125 MHz, CD
3oD): δ=168.3,168.3,163.7,149.6(2 C), 148.1,139.9,133.1(2 C), 126.7,122.2,116.4(2 C), 115.5,107.2(2 C), 105.0,93.2,84.3,79.7,75.0,74.2,73.3,72.6,71.8,65.8,65.3,63.6,57.0(2 C) ppm; HRMS(ESI): 691.1851(calcd. for C
30h
36o
17na [M+Na]
+691.1850).
Claims (2)
1. a method of synthetic Tenuifoliside B, is characterized in that, by following steps, realizes:
(1) respectively with syringic aldehyde (
2), P-hydroxybenzoic acid (
3) be raw material, through ethanoyl protection, make 4-acetoxy-3,5-dimethoxy benzaldehyde (
5) and 4-ABA (
6); Solvent is pyridine, and reaction reagent is diacetyl oxide, and temperature of reaction is solvent refluxing, and the reaction times is 2 hours;
(2) 4-acetoxy-3,5-dimethoxy benzaldehyde (
5) through Knoevenagel condensation reaction, make 4-acetoxy-3,5-dimethoxy-cinnamic acid (
7); Reaction solvent is pyridine, and reaction reagent is propanedioic acid, and catalyzer is piperidines, and holding aqua under the arm is benzene, and temperature of reaction is solvent refluxing, and the reaction times is 3 hours;
(3) 4-acetoxy-3,5-dimethoxy-cinnamic acid (
7) dewater and make 4-acetoxy-3,5-dimethoxy-cinnamic acid acid anhydride (
8); Reaction solvent is anhydrous ethyl acetate, and reaction reagent is triethylamine and triphosgene, and 0 ℃ is reacted 10 minutes, room temperature reaction 25 minutes;
(4) 4-acetoxy-3,5-dimethoxy-cinnamic acid acid anhydride (
8) and sucrose (
4) carry out esterification, obtain 3 '-
o-(4-acetoxy-3,5-dimethoxy-cinnamoyl) sucrose (
9); Reaction solvent is N, dinethylformamide, reaction reagent 4-acetoxy-3,5-dimethoxy-cinnamic acid acid anhydride, catalyzer is cobalt chloride and triethylamine, temperature of reaction is room temperature, reaction times is 1 hour, wherein the mol ratio of sucrose and acid anhydrides is 1:1.3, and the mol ratio of sucrose and sodium hydride is 1:8, and the mol ratio of sucrose and cobalt chloride is 1:0.5;
(5) 3 '-
o-(4-acetoxy-3,5-dimethoxy-cinnamoyl) sucrose (
9) and 4-ABA (
6) carry out light and prolong reaction, obtain 3 '-
o-(4-acetoxy-3,5-dimethoxy-cinnamoyl)-6-
o-(4-acetoxy benzoyl) sucrose (
10); Reaction solvent DMF, reaction reagent is 4-ABA, and catalyzer is triphenyl phosphorus and diisopropyl azodiformate, and temperature of reaction is 75 ℃, and the reaction times is 0.5 hour, wherein 3 '-
othe mol ratio of-(4-acetoxy-3,5-dimethoxy-cinnamoyl) sucrose and 4-ABA is 1:2.5 ~ 3.0,3 '-
othe mol ratio of-(4-acetoxy-3,5-dimethoxy-cinnamoyl) sucrose and triphenyl phosphorus/diisopropyl azodiformate is 1:2.7 ~ 3.2;
(6) 3 '-
o-(4-acetoxy-3,5-dimethoxy-cinnamoyl)-6-
o-(4-acetoxy benzoyl) sucrose (
10) de-acetyl protection base generation target product Tenuifoliside B(
1); Reaction solvent is 80% methyl alcohol, catalyzer is ammonium acetate, and temperature of reaction is room temperature, and the reaction times is 24 hours, 3 '-O-(4-acetoxy-3 wherein, 5-dimethoxy-cinnamoyl)-6-O-(4-acetoxy benzoyl) mol ratio of sucrose and Dibutyltin oxide is 1:8;
Synthetic route of the present invention is as follows:
。
2. the method for a kind of synthetic Tenuifoliside B according to claim 1, is characterized in that, in step (5) 3 '-
othe mol ratio of-(4-acetoxy-3,5-dimethoxy-cinnamoyl) sucrose and 4-ABA is 1:2.5,3 '-
othe mol ratio of-(4-acetoxy-3,5-dimethoxy-cinnamoyl) sucrose and triphenyl phosphorus/diisopropyl azodiformate is 1:2.7.
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Title |
---|
TOSHIO MIYASE ET AL: "Tenuifolioses A-F,Oligosaccharide Multi-esters from the roots of Polygala tenuifolia Willd", 《CHEMICAL AND PHARMACEUTICAL BULLETIN》, vol. 39, no. 11, 25 November 1991 (1991-11-25), pages 3082 - 3084 * |
TOSHIO MIYASE ET AL: "Tenuifolioses G-P,Oligosaccharide Multi-Esters from the Roots of Polygala tenuifolia Willd", 《CHEMICAL AND PHARMACEUTICAL BULLETIN》, vol. 40, no. 10, 25 October 1992 (1992-10-25), pages 2741 - 2748 * |
YUKINOBU IKEYA ET AL: "Four New Phenolic Glycosides from Polygala tenuifolia", 《CHEMICAL AND PHARMACEUTICAL BULLETIN》, vol. 39, no. 10, 25 October 1991 (1991-10-25), pages 2600 - 2605 * |
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