CN103524475A - Method for synthesizing polyhydroxy flavanone thiosemicarbazone Schiff base - Google Patents
Method for synthesizing polyhydroxy flavanone thiosemicarbazone Schiff base Download PDFInfo
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- CN103524475A CN103524475A CN201310493943.8A CN201310493943A CN103524475A CN 103524475 A CN103524475 A CN 103524475A CN 201310493943 A CN201310493943 A CN 201310493943A CN 103524475 A CN103524475 A CN 103524475A
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- flavanone
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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
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/68—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with nitrogen atoms directly attached in position 4
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Abstract
The invention relates to a method for synthesizing polyhydroxy flavanone thiosemicarbazone Schiff base. The method comprises the following steps: taking thiosemicarbazide and 2',4'-dyhydroxy chalcone or a derivative of 2',4'-dyhydroxy chalcone as a raw material, taking glacial acetic acid, polyphosphoric acid or phosphoric acid as a catalyst, firstly, dissolving the raw material into an alcohol-water solvent, further adding a catalyst, backflowing and reacting for 24-36 hours in an oil-bath pot at 70-90 DEG C, subsequently cooling so as to volatilize a part of the solvent, cooling to the room temperature, separating out crystal, performing suction filtration, recrystalizing and purifying by using methanol or ethanol so as to obtain the polyhydroxy flavanone thiosemicarbazone Schiff base. The invention establishes a method for synthesizing the polyhydroxy flavanone thiosemicarbazone Schiff base by condensing 2',4'-dyhydroxy chalcone and the derivative of 2',4'-dyhydroxy chalcone together with thiosemicarbazide at one time, the purposes of shortening the reaction procedure and improving the reaction yield are achieved by selecting an appropriate solvent system and a catalyst system, and a foundation is made for synthesis of a flavone thiosemicarbazone compound. The method is easy to operate, separate and purify, and the yield is 72-83%.
Description
Technical field
The invention belongs to chemical substance synthesis technical field, particularly relate to a kind of one-step method for synthesizing of poly-hydroxy flavanone thiosemicarbazone schiff bases.
Background technology
Chromocor compound is that a class has multiple bioactive natural product, is one of main active ingredient in medicinal plant.Because this compounds has pharmacological action widely, enjoy domestic and international numerous investigators' concern always.Cinnamophenone, as the Yi Ge branch of chromocor compound, is important organic synthesis intermediate, and the cinnamophenone of some hydroxyls shows multiple unique pharmacological action.Cinnamophenone has larger flexibility because of its molecule, and easily and different receptors bind, make they have sterilization, anti-inflammatory, antitumor, anti-HIV, antimutagenic, anti-oxidant, the pharmacologically active such as protect the liver.The cinnamophenone compound of take carries out structural modification and transformation as guide, to initiative newtype drug with to widen flavones range of application significant.
(thiosemicarbazone) compound is because containing N, the S heteroatoms that coordination ability is very strong, can make good part and use, and research shows that (thiosemicarbazone) compound and title complex thereof have sterilization, the physiologically active widely such as antiviral and anticancer.
At present, with thiourea compound, flavonoid compound is carried out structural modification, transforms the extensive concern that has obtained Chinese scholars, as: Pan Chunyue etc., synthetic and sign [J], Central South University's journal (natural science edition) of cinnamophenone (thiosemicarbazone) schiff bases, 2007,38 (1): Liu's 93-97. tinkling of pieces of jades etc., the non-solvent microwave of tetralin ketone thiosemicarbazone is synthetic [J] fast, chemical research and application, 2010,22 (5): 660-664.Serious triumphant etc., the method for the treatment of different things alike synthesis of phenyl benzyl ketone thiosemicarbazone [J], organic chemistry, 2010,30 (2): 299-302.Manisekar?Muthukumar,?Periasamy?Viswanathamurthi*,?Cent.?Eur.?J.?Chem,?2010,?8(1)?:229–240。
Cinnamophenone reacts with thiosemicarbazide compound can synthesizing chalcone (or flavanone) thiosemicarbazone schiff bases.The synthetic general of flavanone thiosemicarbazone schiff bases first reacts cinnamophenone and thiosemicarbazide raw material to generation cinnamophenone thiosemicarbazone compound under a small amount of concentrated hydrochloric acid or acetic acid catalysis, cinnamophenone intramolecular cyclization under the katalysis of sodium-acetate, generates flavanone thiosemicarbazone schiff bases again.With poly-hydroxy cinnamophenone and thiosemicarbazide, through the research of single step reaction synthesis of polyhydroxy flavanone thiosemicarbazone Schiff's base aspect, also do not seen and had report.
Summary of the invention
The present invention improves processing condition, and when having been realized poly-hydroxy cinnamophenone and thiosemicarbazide and carried out condensation by single stage method, ring is closed in the inter-sync of cinnamophenone generation molecule, has synthesized the flavanone Schiff's base that simultaneously comprises flavanone and two kinds of functional groups of thiosemicarbazide.
Concrete technology step of the present invention is: thiosemicarbazide is dissolved in solvent, then add 2 ' and, 4 '-dihydroxyl cinnamophenone or derivatives thereof, add again a part of solvent, then add catalyzer, in 70-90 ℃ of oil bath, reflux, reaction 24-36h, naturally cool to room temperature, utilize remaining temperature to steam solvent, the standing crystallization in ventilation, when crystal no longer increases, carry out suction filtration, obtain thick product, then carry out recrystallization purifying with solvent.For guaranteeing that thiosemicarbazide can fully be dissolved in solvent, utilize ultrasonic wave to promote it fully to dissolve.
Reaction equation is as follows:
2 ', 4 '-dihydroxyl cinnamophenone or derivatives thereof and thiosemicarbazide synthesis of polyhydroxy flavanone thiosemicarbazone reaction expression.
Described 2 ', the mol ratio of 4 '-dihydroxyl cinnamophenone or derivatives thereof and thiosemicarbazide is 1:1 ~ 2.
Described solvent is methanol-water or alcohol-water.
Described thiosemicarbazide and solvent burden ratio are thiosemicarbazide: alcohol: water=1:3 ~ 6:1 ~ 3.
Described catalyzer is Glacial acetic acid or polyphosphoric acid or phosphoric acid.
Describedly add 2 ', after 4 '-dihydroxyl cinnamophenone or derivatives thereof, then the solvent adding is methyl alcohol or ethanol.
The total solvent amount that described whole reaction system adds and catalytic amount volume ratio 8 ~ 10:1.
Described recrystallization solvent for use is methyl alcohol or ethanol.
The present invention is by selecting suitable catalyzer, and the combination of suitable solvent and solute proportioning, realized single stage method synthesis of polyhydroxy flavanone thiosemicarbazone schiff bases, simplified reaction process, shortened the reaction times, improved reaction yield, simplified the object of aftertreatment.Process recovery ratio of the present invention can reach 72 ~ 83%.
Embodiment
Embodiment 1
Get 3 mmol thiosemicarbazide in 50ml round-bottomed flask, add successively that 12ml methyl alcohol and 6ml distilled water are ultrasonic makes it dissolve (about 0.5h), in standing several minutes backward thiosemicarbazide solution, add 2mmol 2 ', 4 ', 4-trihydroxy-cinnamophenone, add 10ml methyl alcohol again, then add Glacial acetic acid 3ml, the proportioning that makes total solvent amount and catalyzer Glacial acetic acid is 9.33:1.Be placed in oil bath pan, control oil bath pan homo(io)thermism at 80 ℃, back flow reaction 24h, stop heating, remove the remaining temperature of prolong utilization and steam after part methyl alcohol, reaction flask is placed in to the ventilation crystallization that freely volatilizees, suction filtration, thick product carries out recrystallization purifying with methyl alcohol, yield 83%.This technique is optimised process.
Embodiment 2
Get 2mmol thiosemicarbazide in 50 ml round-bottomed flasks, add successively that 12ml ethanol and 6ml distilled water are ultrasonic makes it dissolve (approximately 0.5 h), in standing several minutes backward thiosemicarbazide solution, add 2mmol 2 ', 4 ', 4-trihydroxy-cinnamophenone, add 6ml ethanol again, then add polyphosphoric acid catalyzed dose of 3ml, the proportioning of total solvent amount and catalyzer Glacial acetic acid is 8:1.Be placed in oil bath pan.Control oil bath pan homo(io)thermism at 70 ℃, after back flow reaction 36h, stop heating, utilize remaining temperature to steam after part ethanol, reaction flask is placed in to the stink cupboard crystallization that freely volatilizees.Suction filtration, the thick product obtaining, then carry out recrystallization purifying with ethanol, products therefrom yield can reach 76%.
Embodiment 3
Get 3mmol thiosemicarbazide in 50ml round-bottomed flask, add successively that 9ml ethanol and 3ml distilled water are ultrasonic makes to dissolve (approximately 0.5 h), in standing several minutes backward thiosemicarbazide solution, add 1.5mmol 2 ', 4 ', 4-trihydroxy-cinnamophenone, add 18ml ethanol again, then add the phosphoric acid of 3ml, the proportioning of total solvent amount and catalyzer Glacial acetic acid is 10:1.Controlling oil bath pan temperature is 90 ℃, back flow reaction 30h.Stop heating, remove the remaining temperature of prolong utilization and steam after part ethanol, reaction flask is put in to the crystallization that freely volatilizees on windowsill.Be placed in the stink cupboard crystallization that freely volatilizees.Suction filtration, the thick product obtaining, then carry out recrystallization purifying with ethanol.Products therefrom yield can reach 72%.
Claims (8)
1. a method for synthesis of polyhydroxy flavanone thiosemicarbazone schiff bases, processing step is for to be dissolved in thiosemicarbazide in solvent, then add 2 ', 4 '-dihydroxyl cinnamophenone or derivatives thereof, then add a part of solvent, finally add catalyzer, in 70-90 ℃ of oil bath, reflux, reaction 24-36h, naturally cools to room temperature, utilize remaining temperature to steam solvent, the standing crystallization in ventilation, when crystal no longer increases, carries out suction filtration, obtain thick product, then carry out recrystallization purifying with solvent.
2. the method for synthesis of polyhydroxy flavanone thiosemicarbazone schiff bases as claimed in claim 1, it is characterized in that raw material 2 ', 4 '-dihydroxyl cinnamophenone and derivative thereof and thiosemicarbazide mol ratio are 1:1 ~ 2.
3. the method for synthesis of polyhydroxy flavanone thiosemicarbazone schiff bases as claimed in claim 1, the solvent that it is characterized in that thiosemicarbazide is methanol-water or alcohol-water.
4. the method for synthesis of polyhydroxy flavanone thiosemicarbazone schiff bases as claimed in claim 1, the proportioning that it is characterized in that thiosemicarbazide and solvent is thiosemicarbazide: alcohol: water=1:3 ~ 6:1 ~ 3.
5. the method for synthesis of polyhydroxy flavanone thiosemicarbazone schiff bases as claimed in claim 1, is characterized in that catalyzer is Glacial acetic acid or polyphosphoric acid or phosphoric acid.
6. the method for synthesis of polyhydroxy flavanone thiosemicarbazone schiff bases as claimed in claim 1, it is characterized in that adding 2 ', after 4 '-dihydroxyl cinnamophenone or derivatives thereof, then the solvent adding is methyl alcohol or ethanol.
7. the method for synthesis of polyhydroxy flavanone thiosemicarbazone schiff bases as claimed in claim 1, is characterized in that total solvent that whole reaction system adds and the volume ratio 8 ~ 10:1 of catalyzer.
8. the method for synthesis of polyhydroxy flavanone thiosemicarbazone schiff bases as claimed in claim 1, is characterized in that recrystallization solvent for use is methyl alcohol or ethanol.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942514A (en) * | 2012-12-07 | 2013-02-27 | 湖南城市学院 | Ionone keto-double-chalcone thiosemicarbazone and production method thereof |
| CN103193749A (en) * | 2013-04-19 | 2013-07-10 | 中国科学院新疆理化技术研究所 | Preparation method of polyhydroxy flavonoids compound |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942514A (en) * | 2012-12-07 | 2013-02-27 | 湖南城市学院 | Ionone keto-double-chalcone thiosemicarbazone and production method thereof |
| CN103193749A (en) * | 2013-04-19 | 2013-07-10 | 中国科学院新疆理化技术研究所 | Preparation method of polyhydroxy flavonoids compound |
Non-Patent Citations (5)
| Title |
|---|
| A.AITMAMBETOV TE AL.: "The Synthesis of Chalcone and Flavanone Semicarbazones from 1,3- and 1,4-Benzodioxane and 1,5-Benzodioxepane Analogues of Chalcones", 《RUSSIAN JOURNAL OF BIOORGANIC CHEMISTRY》, vol. 28, no. 2, 31 December 2002 (2002-12-31), pages 162 - 164 * |
| KUN HU ET AL.: "Synthesis and antitumor activity of liquiritigenin thiosemicarbazone derivatives", 《EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY》, vol. 45, 6 May 2010 (2010-05-06), pages 3453 - 3458, XP027473641, DOI: doi:10.1016/j.ejmech.2010.04.036 * |
| SILVIO CUNHA ET AL.: "One-pot and catalyst-free synthesis of thiosemicarbazones via multicomponent coupling reactions", 《TETRAHEDRON LETTERS》, vol. 50, 24 February 2009 (2009-02-24), pages 2090 - 2093, XP026011885, DOI: doi:10.1016/j.tetlet.2009.02.134 * |
| YU-JING ZHU ET AL.: "Antityrosinase and Antimicrobial Activities of trans-Cinnamaldehyde Thiosemicarbazone", 《J. AGRIC. FOOD CHEM.》, vol. 57, 22 May 2009 (2009-05-22), pages 5518 - 5523 * |
| 庄肃凯等: "一锅煮法合成苯基苄基酮缩氨基硫脲", 《有机化学》, vol. 30, no. 2, 31 December 2010 (2010-12-31), pages 299 - 302 * |
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Application publication date: 20140122 |