CN104311518B - A kind of preparation method of 6-methyl scutellarin genin - Google Patents

A kind of preparation method of 6-methyl scutellarin genin Download PDF

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CN104311518B
CN104311518B CN201410660948.XA CN201410660948A CN104311518B CN 104311518 B CN104311518 B CN 104311518B CN 201410660948 A CN201410660948 A CN 201410660948A CN 104311518 B CN104311518 B CN 104311518B
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scutellarin
flavone
reaction
benzyloxy
acid
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CN104311518A (en
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李念光
唐于平
段金廒
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Nanjing University of Chinese Medicine
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
    • C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
    • C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
    • C07D311/30—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only not hydrogenated in the hetero ring, e.g. flavones

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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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Abstract

The present invention relates to the field of chemical synthesis, it is specifically related to the preparation of Chinese traditional medicine molecule scutellarin active metabolite, scutellarin hydrolyzation of glucose aldehydic acid molecule under strong acid effect is obtained 4 ', 5, 6, 7 kaempferols, 4 ', 5, 6, 7 kaempferols and bromobenzyl react in the presence of acid binding agent, generate 5, 6 dihydroxy 4 ', 7 benzyloxy flavone, 5 hydroxyl 6 methoxyl groups 4 ' are generated the most in the basic conditions with iodomethane reaction, 7 benzyloxy flavone, last 5 hydroxyl 6 methoxyl groups 4 ', 7 benzyloxy flavone catalytic hydrogenation debenzylation in the presence of palladium carbon obtains 6 methyl scutellarin genin.Step of the present invention is simple, easy purification, mild condition, low cost, and overall yield of reaction is more than 70%, and the product purity of synthesis is high, more than 99.0%, is suitable for technology and produces.

Description

A kind of preparation method of 6-methyl scutellarin genin
Technical field
The present invention relates to the field of chemical synthesis, specifically, the present invention relates to scutellarin active metabolism molecule 6-first The synthesis of base scutellarin genin.
Background technology
6-methyl scutellarin genin is natural product scutellarin active metabolism molecule, has the structure of formula (1).
Breviscapine is the flavonoid active ingredient extracted from natural plants Herba Erigerontis, has breviscapine, oil lamp second Element etc., predominantly scutellarin (content is more than 95%) (Chen Yiyue, Wang Shengtao, Zeng Wenshan, Zhu Yinghong, Fu Yong Prunus mume (sieb.) sieb.et zucc., Jiang Tao. the breviscapine relexation to rat aorta flesh ring. new Chinese medicine and clinical pharmacology .1994,5 (2), 15-19).Last century, Breviscapine from the seventies began to be applied to clinic, and research shows that breviscapine has Have increase blood flow, improve microcirculation, expansion blood vessel, reduce blood viscosity, blood fat reducing, fibrinolysis enhancing, antithrombotic, Antiplatelet aggregation etc. act on, and have at aspects such as treatment cardiovascular and cerebrovascular disease, rheumatic arthritis and apoplexy sequela Significantly curative effect.
The main component scutellarin of breviscapine is easy to metabolism (Ge Qinghua, Zhou Zhen, Zhi Xiaojin, Ma Li in vivo Beautiful, Chen Xiuhua. breviscapine pharmacokinetics in dog body and absolute bioavailability research. Chinese Medicine industry is miscellaneous Will, 2003,34 (12), 618-621) (Feng Fang, Shen Yulan. trace scutellarin SPE-HPLC in human plasma The foundation of/MS/MS and pharmacokinetic studies. Chinese Pharmaceutical Journal .2006,41 (6), 457), one of them active metabolism Thing is 6-methyl scutellarin genin.
Owing to 6-methyl scutellarin genin has pharmacologically active widely, explore its chemosynthesis and be significant. Document (Min-Zhe Shen, Zhi-Hao Shi, Nian-Guang Li, Hao-Tang, Qian-Ping Shi, Yu-Ping Tang,Jian-Ping Yang,Jin-Ao Duan.Efficient Synthesis of 6-O-methyl-scutellarein from Scutellarin via Selective Methylation.Letters in Organic Chemistry,2013,10(10), 733-737.) protect 4 ' initially with diphenyl dichloromethane, 6,7 adjacent diphenol hydroxyls in 5,6,7-kaempferol structure Base, the most again with benzyl protection 4 ' position phenolic hydroxyl group, after removing 6,7 diphenyl methylene protection groups, then protects with benzyl Protecting 7 phenolic hydroxyl groups, the method reaction scheme is long, and purifies and separates difficulty, production efficiency is relatively low, and the cost of production is relatively Height, and reaction temperature when protecting with diphenyl dichloromethane is 175 DEG C, is not suitable for synthesizing 6-methyl oil lamp in a large number B prime aglycon.
Summary of the invention
Goal of the invention: the invention aims to solve the deficiencies in the prior art, it is provided that a kind of 6-methyl oil lamp second The preparation method of element aglycon, the present invention synthesizes 6-methyl scutellarin genin, preparation with scutellarin for initiation material Method step is few, and purification is convenient, low cost, and yield is high, and product purity is high, is suitable for industrialized production.
Technical scheme, in order to realize object above, the technical method that the present invention takes is:
The preparation method of the present invention is following reaction equation:
The preparation method of a kind of 6-methyl scutellarin genin that the present invention provides, specifically includes following steps:
A, it is initiation material by scutellarin, under the catalysis of acid, adds pyrohydrolysis, generate 4 ', 5,6,7-tetrahydroxys yellow Ketone (compound 2)；
B, by the 4 ' of above-mentioned generation, 5,6,7-kaempferol (compound 2) in the presence of acid binding agent with cylite or Benzyl chloride generation nucleophilic substitution, generates 5,6-dihydroxy-4 ', 7-benzyloxy flavone (3)；
C, by the 5,6-dihydroxy-4 of above-mentioned generation ', 7-benzyloxy flavone (3) in the presence of acid binding agent with iodomethane Reaction, generates 5-hydroxyl-6-methoxyl group-4 ', 7-benzyloxy flavone (4)；
D, by the 5-hydroxyl-6-methoxyl group-4 of above-mentioned generation ', 7-benzyloxy flavone (4) passes through in the presence of palladium carbon Catalytic hydrogenation removing benzyl obtains 6-methyl scutellarin genin (compound 1).
Above-mentioned reaction a step reaction solvent selects concentration to be the ethanol of 95%.
Above-mentioned reaction a step use concentrated acid be the one in mineral acid such as concentrated sulphuric acid, concentrated hydrochloric acid, concentrated nitric acid or it Mixture.
Above-mentioned reaction b or step c one or more organic solvent the most following react: DMF (N, N-bis- Methylformamide), acetone, acetonitrile, ethanol, chloroform, ethyl acetate, further preferred DMF (N, N-diformazan Base Methanamide) or acetone.
Above-mentioned reaction Step d reaction dissolvent is selected from oxolane, ethanol, methanol, ethyl acetate or N, N-dimethyl The preferred potassium carbonate of Methanamide acid binding agent, potassium bicarbonate, sodium carbonate, sodium bicarbonate.
In above-mentioned reaction, a step reaction temperature preferably 50～140 DEG C, further preferred 70～120 DEG C, b step and The reaction temperature of step c preferably 10～150 DEG C, further preferred 30～60 DEG C.
Step a, b and c reaction system are preferably pressed into protective gas nitrogen or argon.
Wherein preferred 0.05g/ml～0.1g/ml of scutellarin concentration in alcoholic solution in a step, inorganic acid alcohol is molten The concentration of liquid preferably 3～8mol/L, further preferred scutellarin concentration 0.07g/ml in alcoholic solution, inorganic acid alcohol Concentration 5mol/L of solution.
4 ', 5,6,7-kaempferols and cylite or preferred 1:2～1:3 of mol ratio of benzyl chloride in step b, further Preferably 1:2.3；
In step c 5,6-dihydroxy-4 ', 7-benzyloxy flavone and preferred 1:1～1:2 of mol ratio of iodomethane, enter one Walk preferred 1:1.3；
5-hydroxyl-6-methoxyl group-4 in step d ', 7-benzyloxy flavone and preferred 1:0.05～1:1 of weight ratio of palladium carbon, Further preferably 1:0.1.
Beneficial effect: compared to the prior art, the present invention has the following advantages:
Compared to the prior art, reactions steps is simple for the present invention, and purification is convenient, and production efficiency is high, mild condition, Overall yield of reaction is more than 70%, and low cost, the product purity of synthesis is high, more than 99.0%, is suitable for technology and produces.
Accompanying drawing explanation
Fig. 1 is the structural representation of 6-methyl scutellarin genin of the present invention.
Fig. 2 is the reacting flow chart of 6-methyl scutellarin genin preparation method of the present invention.
Detailed description of the invention
According to following embodiment, the present invention be may be better understood.But, as it will be easily appreciated by one skilled in the art that Concrete material proportion, process conditions and result thereof described by embodiment are merely to illustrate the present invention, and should not Also without limitation on the present invention described in detail in claims.
Embodiment 1
The preparation of 4 ', 5,6,7-kaempferol (2)
Scutellarin 50 is added in the 1000ml reaction bulb pouring pipe equipped with mechanical agitator, thermometer and nitrogen into G, 3mol L-190% concentrated sulphuric acid ethanol solution 500mL, be passed through nitrogen displaced air, be heated to 120 DEG C, Reaction 48h, reaction cools down after terminating, and reactant liquor is poured in 4L water, sucking filtration, and filter cake is washed to neutrality, 50 DEG C It is dried.Filter cake obtains yellow solid 26.3g, yield 85.5% with the ethanol recrystallization repeatedly of 50%.
Structure elucidation is1H NMR(300MHz,DMSO-d6)δ:6.78(s,1H,C3-H),6.73(s,1H,C8-H), 6.92 (d, J=8.8Hz, 2H, C3′,C5′-H), 7.92 (d, J=8.8Hz, 2H, C2′,C6′-H),8.71(s,1H,C6-OH), 10.30(s,1H,C4′-OH),10.44(s,1H,C7-OH),12.79(s,1H,C5-OH).ESI-MS:m/z 285 [M-H]-。
5,6-dihydroxy-4 ', the preparation of 7-benzyloxy flavone (3)
84g compound 2 is added in equipped with the 1000ml reaction bulb of mechanical agitator, thermometer and nitrogen ingress pipe, DMF500ml, K2CO3109g, bromobenzyl 80mL, be passed through nitrogen displaced air, after room temperature reaction 12h, instead Answer liquid 2000ml ethyl acetate to extract, then wash, methacrylate layer with 1000ml saline wash, methacrylate layer without Water Na2SO4Being dried, filter, filtrate concentrates, and concentrate obtains yellow solid 128 with the ethanol recrystallization repeatedly of 50% G, yield 93%.
Structure elucidation is1H NMR(300MHz,DMSO-d6)δ13.11(s,1H,5-OH),10.82(s,1H, 6-OH), 8.04 (d, 2H, J=8.6Hz, 2 ', 6 '-H), 7.31-7.53 (m, 10H ,-Ph), 7.18 (d, 2H, J=8.6Hz, 3′,5′-H),6.87(s,1H,8-H),6.62(s,1H,3-H),5.23(s,2H,-OCH2),5.03(s,2H,-OCH2)； ESI-MS:m/z 465[M-H]-.
5-hydroxyl-6-methoxyl group-4 ', the preparation of 7-benzyloxy flavone (4)
84g compound is added in equipped with the 1000ml reaction bulb of mechanical agitator, thermometer and nitrogen ingress pipe 3, DMF 200ml, K2CO348g, iodomethane 14ml, be passed through nitrogen displaced air, after room temperature reaction 12h, Reactant liquor 500ml ethyl acetate is extracted, and then washes, methacrylate layer
200 saline washings, methacrylate layer anhydrous Na2SO4Being dried, filter, filtrate concentrates, concentrate 50% ethanol Recrystallization, finally obtains compound as yellow solid 81g, yield 94%.
Structure elucidation is:1H NMR(300MHz,DMSO-d6) δ 12.69 (s, 1H, 5-OH), 7.94 (d, 2H, J= 8.6Hz,2′,6′-H),7.44-7.54(m,4H,-Ph),7.32-7.42(m,6H,-Ph),7.00(s,1H,8-H),6.94(d, 2H, J=8.6Hz, 3 ', 5 '-H), 6.62 (s, 1H, 3-H), 5.28 (s, 2H ,-OCH2),4.95(s,2H,-OCH2),4.00 (s,3H,-OCH3)；ESI-MS:m/z 481[M+H]+.
The preparation of 6-methyl scutellarin genin (compound 1)
Compound 5-hydroxyl-6-methoxyl group-4 is added in equipped with 1000ml mono-neck bottle of magnetic stirring apparatus ', 7-dibenzyl Epoxide flavone (4) 100g, in the mixed solution of dehydrated alcohol 250ml and THF 250ml, is subsequently adding 10% Pd/C 2g, is passed through hydrogen exchange air, room temperature reaction 8h, reacts after terminating, and reacting liquid filtering concentrates, dense Contracting thing obtains yellow solid (compound 1) 60g, yield 96% with 50% ethyl alcohol recrystallization.
Structure elucidation:1H NMR(300MHz,DMSO-d6)δ12.76(s,1H,5-OH),10.72(s,1H, 7-OH), 10.19 (s, 1H, 4 '-OH), 7.87 (d, 2H, J=8.6Hz, 2 ', 6 '-H), 6.89 (d, 2H, J=8.6Hz, 3′,5′-H),7.11(s,1H,8-H),6.58(s,1H,3-H),3.72(s,3H,-OCH3)；ESI-MS:m/z 299 [M-H]-.
Embodiment 2
The preparation of 4 ', 5,6,7-kaempferol (2)
Scutellarin 50 is added in the 1000ml reaction bulb pouring pipe equipped with mechanical agitator, thermometer and nitrogen into G, 3mol L-190% concentrated sulphuric acid ethanol solution 500mL, be passed through nitrogen displaced air, be heated to 120 DEG C, Reaction 48h, reaction cools down after terminating, and reactant liquor is poured in 4L water, sucking filtration, and filter cake is washed to neutrality, 50 DEG C It is dried.Filter cake obtains yellow solid 26.3g, yield 85.5% with the ethanol recrystallization repeatedly of 50%.
Structure elucidation is1H NMR(300MHz,DMSO-d6)δ:6.78(s,1H,C3-H),6.73(s,1H,C8-H), 6.92 (d, J=8.8Hz, 2H, C3′,C5′-H), 7.92 (d, J=8.8Hz, 2H, C2′,C6′-H),8.71(s,1H,C6-OH), 10.30(s,1H,C4′-OH),10.44(s,1H,C7-OH),12.79(s,1H,C5-OH).ESI-MS:m/z 285 [M-H]-。
5,6-dihydroxy-4 ', the preparation of 7-benzyloxy flavone (3)
84g compound 2 is added in equipped with the 1000ml reaction bulb of mechanical agitator, thermometer and nitrogen ingress pipe, Acetone 500ml, K2CO3109g, bromobenzyl 80mL, be passed through nitrogen displaced air, after back flow reaction 8h, instead Answering liquid to filter, filtrate concentrates, and concentrate obtains yellow solid 124g, yield 90% with the ethanol recrystallization repeatedly of 50%.
5-hydroxyl-6-methoxyl group-4 ', the preparation of 7-benzyloxy flavone (4)
84g compound is added in equipped with the 1000ml reaction bulb of mechanical agitator, thermometer and nitrogen ingress pipe 3, acetone 200ml, K2CO348g, iodomethane 14ml, be passed through nitrogen displaced air, after back flow reaction 10h, Reacting liquid filtering, filtrate concentrates, concentrate 50% ethyl alcohol recrystallization, finally obtains compound as yellow solid 79g, Yield 92%.
The preparation of 6-methyl scutellarin genin (compound 1)
Compound 5-hydroxyl-6-methoxyl group-4 is added in equipped with 1000ml mono-neck bottle of magnetic stirring apparatus ', 7-dibenzyl Epoxide flavone (4) 100g, dehydrated alcohol 500ml, be subsequently adding 10%Pd/C 2g, is passed through hydrogen exchange air, Room temperature reaction 8h, after reaction terminates, reacting liquid filtering, concentrate, it is solid that concentrate obtains yellow with 50% ethyl alcohol recrystallization Body ((compound 1)) 58g, yield 92%.
Structure elucidation:1H NMR(300MHz,DMSO-d6)δ12.76(s,1H,5-OH),10.72(s,1H, 7-OH), 10.19 (s, 1H, 4 '-OH), 7.87 (d, 2H, J=8.6Hz, 2 ', 6 '-H), 6.89 (d, 2H, J=8.6Hz, 3′,5′-H),7.11(s,1H,8-H),6.58(s,1H,3-H),3.72(s,3H,-OCH3)；ESI-MS:m/z 299 [M-H]-.
Embodiment 3
The preparation of 4 ', 5,6,7-kaempferol (2)
Scutellarin 50 is added in the 1000ml reaction bulb pouring pipe equipped with mechanical agitator, thermometer and nitrogen into G, 3mol L-190% concentrated sulphuric acid ethanol solution 500mL, be passed through nitrogen displaced air, be heated to 120 DEG C, Reaction 48h, reaction cools down after terminating, and reactant liquor is poured in 4L water, sucking filtration, and filter cake is washed to neutrality, 50 DEG C It is dried.Filter cake obtains yellow solid 26.3g, yield 85.5% with the ethanol recrystallization repeatedly of 50%.
Structure elucidation is1H NMR(300MHz,DMSO-d6)δ:6.78(s,1H,C3-H),6.73(s,1H,C8-H), 6.92 (d, J=8.8Hz, 2H, C3′,C5′-H), 7.92 (d, J=8.8Hz, 2H, C2′,C6′-H),8.71(s,1H,C6-OH), 10.30(s,1H,C4′-OH),10.44(s,1H,C7-OH),12.79(s,1H,C5-OH).ESI-MS:m/z 285 [M-H]-。
5,6-dihydroxy-4 ', the preparation of 7-benzyloxy flavone (3)
84g compound 2 is added in equipped with the 1000ml reaction bulb of mechanical agitator, thermometer and nitrogen ingress pipe, Acetone 500ml, Na2CO384g, bromobenzyl 80mL, be passed through nitrogen displaced air, after back flow reaction 8h, instead Answering liquid to filter, filtrate concentrates, and concentrate obtains yellow solid 126g, yield 92% with the ethanol recrystallization repeatedly of 50%.
5-hydroxyl-6-methoxyl group-4 ', the preparation of 7-benzyloxy flavone (4)
84g compound is added in equipped with the 1000ml reaction bulb of mechanical agitator, thermometer and nitrogen ingress pipe 3, acetone 200ml, Na2CO337g, iodomethane 14ml, be passed through nitrogen displaced air, back flow reaction 10h After, reacting liquid filtering, filtrate concentrates, concentrate 50% ethyl alcohol recrystallization, finally obtains compound as yellow solid 80 G, yield 93%.
The preparation of 6-methyl scutellarin genin (compound 1)
Compound 5-hydroxyl-6-methoxyl group-4 is added in equipped with 1000ml mono-neck bottle of magnetic stirring apparatus ', 7-dibenzyl Epoxide flavone (4) 100g, dehydrated alcohol 500ml, be subsequently adding 10%Pd/C 2g, is passed through hydrogen exchange air, Room temperature reaction 8h, after reaction terminates, reacting liquid filtering, concentrate, it is solid that concentrate obtains yellow with 50% ethyl alcohol recrystallization Body ((compound 1)) 58g, yield 92%.
Structure elucidation:1H NMR(300MHz,DMSO-d6)δ12.76(s,1H,5-OH),10.72(s,1H, 7-OH), 10.19 (s, 1H, 4 '-OH), 7.87 (d, 2H, J=8.6Hz, 2 ', 6 '-H), 6.89 (d, 2H, J=8.6Hz, 3′,5′-H),7.11(s,1H,8-H),6.58(s,1H,3-H),3.72(s,3H,-OCH3)；ESI-MS:m/z 299 [M-H]-.
Embodiment of above only for technology design and the feature of the present invention are described, its object is to allow and is familiar with technique People understand present invention and be carried out, can not limit the scope of the invention with this, all according to this The equivalence that bright spirit is done changes or modifies, and all should contain within the scope of the present invention.

Claims (1)

1. the preparation method of a 6-methyl scutellarin genin, it is characterised in that comprise the following steps:
A, taking scutellarin hydrolysis occurs in presence of an acid, removing glucuronic acid generates 4 ', 5,6,7- Kaempferol；
B, by 4 ', 5,6,7-kaempferol in the presence of acid binding agent with cylite or benzyl chloride generation nucleophilic displacement of fluorine Reaction, generates generation 5,6-dihydroxy-4 ', 7-benzyloxy flavone；
C, by 5,6-dihydroxy-4 ', 7-benzyloxy flavone in the presence of acid binding agent with iodomethane reaction, generate 5-hydroxyl-6-methoxyl group-4 ', 7-benzyloxy flavone；
D, by 5-hydroxyl-6-methoxyl group-4 ', 7-benzyloxy flavone, catalytic hydrogenation debenzylation in the presence of palladium carbon Obtain 6-methyl scutellarin genin；
Step a reaction dissolvent be volumetric concentration be the ethanol of 95%；
Acid used by step a is a kind of in sulphuric acid, hydrochloric acid, nitric acid or their mixture；Step a is reacted Temperature is 70～120 DEG C；
Step b or step c reaction dissolvent be N,N-dimethylformamide, acetone, acetonitrile, ethanol, chloroform, One or more in ethyl acetate；
The reaction temperature of step b or c is 30～60 DEG C；
Acid binding agent in step b is potassium carbonate, sodium carbonate, potassium bicarbonate or sodium bicarbonate；
Step d reaction dissolvent is oxolane, ethanol, methanol, ethyl acetate or N,N-dimethylformamide；
Step a, b, c reaction are passed through nitrogen or argon, step d is passed through hydrogen；
In step a, scutellarin concentration in alcoholic solution is 0.07g/ml, and the concentration of mineral acid alcoholic solution is 5mol/L；
In step b 4 ', 5,6,7-kaempferol is 1:2.3 with the mol ratio of cylite or benzyl chloride；
5,6-dihydroxy-4 in step c ', 7-benzyloxy flavone is 1:1.3 with the mol ratio of iodomethane；
5-hydroxyl-6-methoxyl group-4 in step d ', 7-benzyloxy flavone is 1:0.1 with the weight ratio of palladium carbon.
CN201410660948.XA 2014-11-18 2014-11-18 A kind of preparation method of 6-methyl scutellarin genin Expired - Fee Related CN104311518B (en)

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