CN103360227A - Fluorenone derivative and preparation method thereof - Google Patents
Fluorenone derivative and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a fluorenone derivative and a preparation method thereof. The fluorenone derivative is a poly-substituted fluorenone derivative, and the preparation method of the fluorenone derivative comprises the following steps: a, the synthesis of a substrate; b, the catalysis by palladium, and C, the purification of a product. The fluorenone derivative can be used as a precursor in a synthesis and development process of a medicament, and the structural specificity of the fluorenone derivative endows the fluorenone derivative with certain use value in the field of organic synthesis.
Description
Technical field
The present invention relates to a kind of fluorenone derivatives and preparation method thereof, be used in particular for synthetic condensed ring.
Background technology
According to U.S.'s medical report of nineteen ninety-five, surpass 80% clinical medicine at American market and comprise at least one ring.And in many natural products, ring texture also is one of its essential condition.In view of the special significance of ring compound, how to go to construct ring texture and caused that countless organic synthesis men and chemist actively think deeply, and drawn some effectively methods.The method of common synthesis of cyclic compound has:
1) intramolecular nucleophilic substitution reaction: open chain compound intramolecular cyclization
By intramolecular S
N2 remove to construct ring compound, this kind method can more effectively be synthesized more stable five yuan and six-membered cyclic compound, but the concentration of alkali can affect the carrying out of reaction, and follows emulative elimination reaction, thereby the productive rate of reaction is descended, and bring certain trouble for the separation of product.
2) cycloaddition reaction: two or more undersaturated compounds form ring by the restructuring of electronics.Wherein most typical is exactly Diels-Alder reaction:
Diels-Alder reaction be conjugated dienes system and alkene or the addition reaction of acetylene bond initial ring and the reaction of tetrahydrobenzene or 1，4-cyclohexadiene ring system.In the reaction of this class, be called dienophile with alkene and the alkynes of conjugated dienes effect.The effect of having the reaction of making to accelerate for electron substituent group on electron-withdrawing substituent on the dienophile (such as carbonyl, cyano group, nitro, carboxyl etc.) and the conjugated dienes.
Diels-Alder reaction has abundant stereochemistry to present, and has stereoselectivity, stereospecificity and regioselectivity etc. concurrently.When diene and dienophile both have suitable substituting group, make reaction that different positions may occur and when obtaining two kinds of products, it is main in fact only having a kind of.This reaction by conjugated dienes and alkene or alkynes reaction generation six-ring is one of means of very important C―C bond formation in the organic chemical synthesis reaction, also is one of reaction commonly used in the modern organic synthesis.
In addition the cycloaddition reaction that is applied also has [2+2] cycloaddition reaction, can be used for synthetic tetra-atomic ring.
3) diekmann condensation reaction: diester issues the reaction that sub-internal condensation estranged generates 'beta '-ketoester in the alkali effect.
In this reaction, the alkali in the solution is at first captured the α-hydrogen of ester carbonyl group, the Formed negative ion, because carbanion is unstable, and will another carbonyl carbon of attack, addition reaction occurs, the alcoxyl negative ion is left away simultaneously.Alkali is captured a α-hydrogen more afterwards, irreversibly generates stable enol negative ion, obtains product finally by acid treatment.
4) Robinson's annulation: contain cyclic ketones and a of active methylene group, the b-beta-unsaturated carbonyl compounds reacts in the presence of alkali, forms one the two also ring system of six membered ring:
This reaction was divided into for two steps, and the first step is the Micheal addition reaction, and second step is aldol reaction.When the reaction beginning, Michael addition occurs in the alpha, beta-unsaturated ketone of enolate nucleophilic attack by carbonyl compound of alkali attack generates.The product that generates carries out aldol condensation in the molecule immediately under the highly basic condition, obtain Robinson's annulation product.
5) the synthetic monocycle of the carbon-hydrogen bond activation of metal catalytic or polynuclear compound
The organic synthesis that is undertaken by carbon-hydrogen bond activation is rapidly popular domain of development in recent years.By the activation of hydrocarbon key, can effectively realize the formation of carbon-carbon bond, thereby construct the compound of more complicated.Therefore the direct functionalization reaction of hydrocarbon key is described as " Holy grail of chemistry " owing to having multiple outstanding advantage and very large challenge, attracts more and more scientists' concern.And the method that the most effectively realizes carbon-hydrogen bond activation is transition metal-catalyzed cross-coupling reaction.Such as Suzuki reaction, Heck reaction, Domino reaction etc., at present after deliberation very ripe.And in these cross-coupling reactions, palladium catalyst plays vital effect undoubtedly.Following for example, the just catalysis by palladium catalyst in the molecule and intermolecular Heck reaction, realizes the carbon-hydrogen bond activation of acetylene bond, a step forms three new carbon-carbon bonds, has formed new six-ring compound.From having saved in essence reactions steps, improved the utilization ratio of atom.
Summary of the invention
The object of the present invention is to provide a kind of fluorenone derivatives and preparation method thereof, concrete technical scheme is as follows:
A kind of fluorenone derivatives, its structural formula of described fluorenone derivatives is:
Described R
1Be hydrogen or fluorine, R
2Be hydrogen, methyl, ethyl, methoxyl group or oxyethyl group etc.
Further, the structural formula of described Fluorenone is:
Described R
1, R
2Hydrogen.
Further, it is polysubstituted fluorenone derivatives.
Further, it is the efficient synthetic fluorenone derivatives that contains condensed ring.
The preparation method of above-mentioned fluorenone derivatives comprises the steps:
Synthesizing of a, substrate;
B, palladium catalysis;
The purifying of c, product.
Further, step a comprises the steps:
(1) adds methyl alcohol in the adjacent bromoacetophenone as solvent;
(2) NaOH solution is directly poured into and is stirred, and drips phenylacrolein;
(3) drip after, add rinse liquid and reaction;
(4) remove reaction, washing, ethyl acetate extraction, the organic phase anhydrous magnesium sulfate drying is spin-dried for, and the column chromatography for separation crude product gets white solid stand-by;
(5) Pd (PhCN)
2Cl
2Place container with CuI, three take out three fill after, under the condition of inflation, add phenylacetylene and P (t-Bu)
3Skellysolve A solution;
(6) after the stirring, add diisopropylamine, and add rinse liquid;
(7) reinforced complete after, keep the inflated condition reaction;
(8) remove reaction, use ethyl acetate extraction;
(9) boil off solvent, column chromatography separates, and gets faint yellow solid stand-by.
Further, step a comprises:
The 250mL three-necked bottle is contained on the mechanical stirrer, adds 9.95 g(50 mmol in the bottle) adjacent bromoacetophenone, add again 30mL methyl alcohol as solvent; Measure approximately 50mL 15% NaOH solution and directly pour into, stir 2 min after, under the condition of ice-water bath, drip 6.6g(50mmol with constant pressure funnel) phenylacrolein; After dripping, with methyl alcohol rinse dropping funnel, rinse liquid liquid adds in the reaction flask, reacts approximately 3h, removes reaction, washing, ethyl acetate extraction, the organic phase anhydrous magnesium sulfate drying is spin-dried for, the column chromatography for separation crude product gets approximately 14.09 g of white solid, and productive rate 90% is stand-by;
Reaction substrate 1a: weigh 3.13 g (10 mmol) 1.115 mg (0.3 mmol) Pd (PhCN)
2Cl
2Place 50 mL Schlenk bottles with 38 mg (0.2 mmol) CuI, three take out three fill after, under the condition of inflation, add 1.25 g (12 mmol) phenylacetylene and the about P of 2 ml 10% (t-Bu) with syringe
3Skellysolve A solution; Under the condition of ice-water bath, stir half an hour after, add 1.23 g (12 mmol) diisopropylamine, add the syringe Isosorbide-5-Nitrae-dioxane rinse of phenylacetylene and tri-butyl phosphine, rinse liquid adds reactor, after reinforced complete, keep inflated condition reaction 12h; Remove reaction, use ethyl acetate extraction; Boil off solvent, column chromatography separates, and gets faint yellow solid 2.44 g (7.3 mmol), and productive rate 73% is stand-by.
Further, step b comprises the steps:
In container, add successively reaction substrate 1a, Pd (OAc)
2
Three take out three fills rear adding 3-propargyl bromide, 0.5 mL tri-n-butylamine, DMF;
Be stirred to homogeneous phase under argon gas atmosphere, heat and magnetic agitation to there being palladium black to separate out.
Further, step b comprises the steps: in the Schlenk bottle of 25 mL dryings, adds successively 0.334 g (1 mmol) reaction substrate 1a, 4.8 mg (0.02 mmol) Pd (OAc)
2, three take out three fills and adds 0.143 g (1.2 mmol) 3-propargyl bromide with syringe afterwards, 0.5 mL tri-n-butylamine, and 5 mL DMF stir and are heated to 140 ℃ to homogeneous phase under argon gas atmosphere half an hour, and magnetic agitation 18 h are to there being palladium black to separate out.
Further, step c comprises the steps: stopped reaction, after the question response miscellany is cooled to room temperature, pours in the 15 mL water and extracts with ethyl acetate 3 * 10 mL, organic layer is used 15 ml5% dilute hydrochloric acid, 15ml5% yellow soda ash and 15 mL saturated common salt water washings, anhydrous magnesium sulfate drying successively; Filter, vacuum boils off solvent, and crude product separates to get pure compound with column chromatography.
Compare with present prior art, a kind of synthetic method of brand-new Fluorenone is provided, generate a series of new fluorenone derivatives.One of Fluorenone main application is the raw material as the functional polymer monomer, and bisphenol fluorene namely is wherein a kind of.Be that the fluorenes resin that raw material is made has very good characteristics by Fluorenone, high such as transparency, specific refractory power is high, good heat resistance, and it is good to be dissolved in the solvent rear formability, is used as the epoxy resin modification agent, improves second-order transition temperature and the physical strength of Resins, epoxy.The derivative of Fluorenone is that sensitive materials is its another important applied field as non-silver.The Imaging Principle of this class sensitive materials is, makes first material charged, again charged materials carried out image exposure, obtains permanent image through developing fixing.Fluorenone also can synthesize multi-medicament as medicine intermediate.
Fluorenone derivatives of the present invention can be used as the precursor in the synthetic and exploitation of medicine; And because the singularity of its structure may make it in the organic synthesis field certain utility value also be arranged.
Description of drawings
Fig. 1 is fluorenone derivatives structural formula of the present invention
Fig. 2 a, 2b, 2c, 2d are the proton nmr spectra of the embodiment of the invention
Embodiment
The below describes the present invention with reference to the accompanying drawings, and it is a kind of preferred embodiment in the numerous embodiments of the present invention.
A kind of fluorenone derivatives, its structural formula is:
Described R
1Be hydrogen, fluorine, R2 is hydrogen, methyl, ethyl, methoxyl group, oxyethyl group etc.
The structural formula of preferred Fluorenone is:
Be described R
1, R
2, R
3Hydrogen
Preparation method of the present invention is: the purifying of synthetic, the b of a, substrate, palladium catalysis, c, product.
Synthesizing of a, substrate: substrate synthetic in two steps: 250 mL three-necked bottles are contained on the mechanical stirrer, add 9.95 g(50 mmol in the bottle) adjacent bromoacetophenone, add again 30mL methyl alcohol as solvent.Measuring approximately 50 mL, 15% NaOH solution directly pours into, after stirring 2 min, under the condition of ice-water bath, drip 6.6g(50mmol with constant pressure funnel) phenylacrolein (using solvent cut), after dripping, with methyl alcohol rinse dropping funnel, rinse liquid liquid adds in the reaction flask, react approximately 3 h, remove reaction, washing, ethyl acetate extraction, the organic phase anhydrous magnesium sulfate drying, be spin-dried for column chromatography for separation crude product (EA:PE=1:40), get approximately 14.09 g of white solid, productive rate 90%, stand-by.The 2nd, by synthesizing of substrate 1a, weigh 3.13 g (10 mmol) 1,115 mg (0.3 mmol) Pd (PhCN)
2Cl
2Place 50 mL Schlenk bottles with 38 mg (0.2 mmol) CuI, three take out three fill after, under the condition of inflation, add 1.25 g (12 mmol) phenylacetylene and the about P of 2 ml 10% (t-Bu) with syringe
3Skellysolve A solution.Under the condition of ice-water bath, stir half an hour after, add 1.23 g (12 mmol) diisopropylamine, add the syringe Isosorbide-5-Nitrae-dioxane rinse of phenylacetylene and tri-butyl phosphine, rinse liquid adds reactor, after reinforced complete, keep inflated condition reaction 12h.Remove reaction, use ethyl acetate extraction.Boil off solvent, column chromatography separates that (eluent is EA/PE=1:20), get faint yellow solid 2.44 g (7.3 mmol), and productive rate 73% is stand-by.
B, palladium catalysis are: in the Schlenk bottle of 25 mL dryings, add successively 0.334 g (1 mmol) reaction substrate 1a, 4.8 mg (0.02 mmol) Pd (OAc)
2, three take out three fills and adds 0.143 g (1.2 mmol) 3-propargyl bromide, 0.5 mL tri-n-butylamine, 5 mL DMF with syringe afterwards.Stir and be heated to 140 ℃ to homogeneous phase under argon gas atmosphere half an hour, magnetic agitation 18 h are to there being palladium black to separate out.
The purifying of c, product is: stopped reaction, after the question response miscellany is cooled to room temperature, pour in the 15 mL water and extract with ethyl acetate 3 * 10 mL, organic layer is used 15 ml dilute hydrochloric acid (5%), 15ml yellow soda ash (5%) and 15 mL saturated common salt water washings, anhydrous magnesium sulfate drying successively.Filter, vacuum boils off solvent, and crude product separates to get pure compound (EA/PE=1:8) with column chromatography.
In a further advantageous embodiment, Fluorenone synthetic: shown on the synthetic route: substrate synthetic in two steps: 250 mL three-necked bottles are contained on the mechanical stirrer, adding 9.95 g(50 mmol in the bottle) adjacent bromoacetophenone adds 30mL methyl alcohol again as solvent.Measuring approximately 50 mL, 15% NaOH solution directly pours into, after stirring 2 min, under the condition of ice-water bath, drip 6.6g(50mmol with constant pressure funnel) phenylacrolein (using solvent cut), after dripping, with methyl alcohol rinse dropping funnel, rinse liquid liquid adds in the reaction flask, react approximately 3 h, remove reaction, washing, ethyl acetate extraction, the organic phase anhydrous magnesium sulfate drying, be spin-dried for column chromatography for separation crude product (EA:PE=1:40), get approximately 14.09 g of white solid, productive rate 90%, stand-by.The 2nd, by synthesizing of substrate 1a, weigh 3.13 g (10 mmol) 1,115 mg (0.3 mmol) Pd (PhCN)
2Cl
2Place 50 mL Schlenk bottles with 38 mg (0.2 mmol) CuI, three take out three fill after, under the condition of inflation, add 1.25 g (12 mmol) phenylacetylene and the about P of 2 ml 10% (t-Bu) with syringe
3Skellysolve A solution.Under the condition of ice-water bath, stir half an hour after, add 1.23 g (12 mmol) diisopropylamine, add the syringe Isosorbide-5-Nitrae-dioxane rinse of phenylacetylene and tri-butyl phosphine, rinse liquid adds reactor, after reinforced complete, keep inflated condition reaction 12h.Remove reaction, use ethyl acetate extraction.Boil off solvent, column chromatography separates that (eluent is EA/PE=1:20), get faint yellow solid 2.44 g (7.3 mmol), and productive rate 73% is stand-by.B, palladium catalysis are: in the Schlenk bottle of 25 mL dryings, add successively 0.334 g (1 mmol) reaction substrate 1a, 4.8 mg (0.02 mmol) Pd (OAc)
2, three take out three fills and adds 0.143 g (1.2 mmol) 3-propargyl bromide, 0.5 mL tri-n-butylamine, 5 mL DMF with syringe afterwards.Stir and be heated to 140 ℃ to homogeneous phase under argon gas atmosphere half an hour, magnetic agitation 18 h are to there being palladium black to separate out.The purifying of c, product is: stopped reaction, after the question response miscellany is cooled to room temperature, pour in the 15 mL water and extract with ethyl acetate 3 * 10 mL, organic layer is used 15 ml dilute hydrochloric acid (5%), 15ml yellow soda ash (5%) and 15 mL saturated common salt water washings, anhydrous magnesium sulfate drying successively.Filter, vacuum boils off solvent, and crude product separates to get pure compound (EA/PE=1:8) with column chromatography.
The structure of Fluorenone is passed through;
1H NMR;
13C NMR; HRMS; IR measures.1H?NMR?(300?MHz,?CDCl
3):?δ?7.74?(d,?J?=?7.8?Hz,?1H),?7.65?(d,?J?=?7.2?Hz,?1H),?7.30-7.42?(m,?4H),?7.12-7.23?(m,?6H),?7.01-7.14?(m,?3H),6.23?(d,?J?=?7.2?Hz,?1H);?
13C?NMR?(75?MHz,?CDCl
3):?δ?193.55,?148.53,?144.60,?142.36,?140.19,?137.86,?136.69,?134.92,?134.42,?133.54,?130.76,?130.02,?129.47,?128.56,?127.72,?127.08,?123.99,?123.36,?123.28?ppm;
HRMS?(EI):?m/z?[M]
+?calcd?for?C25H16O:?332.1201;?found:?332.1206.
FT-IR?(KBr):?ν?1707,?1599,?1462,?1294,?1163,?935,?848,?765,?752,?700?cm
-1;
The present invention compared with prior art provides a kind of synthetic method of brand-new Fluorenone, generates a series of new fluorenone derivatives.One of Fluorenone main application is the raw material as the functional polymer monomer, and bisphenol fluorene namely is wherein a kind of.Be that the fluorenes resin that raw material is made has very good characteristics by Fluorenone, high such as transparency, specific refractory power is high, good heat resistance, and it is good to be dissolved in the solvent rear formability, is used as the epoxy resin modification agent, improves second-order transition temperature and the physical strength of Resins, epoxy.The derivative of Fluorenone is that sensitive materials is its another important applied field as non-silver.The Imaging Principle of this class sensitive materials is, makes first material charged, again charged materials carried out image exposure, obtains permanent image through developing fixing.Fluorenone also can synthesize multi-medicament as medicine intermediate.Fluorenone derivatives in the application prospect in organic synthesis field still very widely thus.
The above has carried out exemplary description to the present invention by reference to the accompanying drawings; obviously specific implementation of the present invention is not subjected to the restriction of aforesaid way; as long as the various improvement of having adopted method design of the present invention and technical scheme to carry out; or directly apply to other occasion without improvement, all within protection scope of the present invention.
Claims (10)
1. a fluorenone derivatives is characterized in that, its structural formula of described fluorenone derivatives is:
Described R
1Be hydrogen or fluorine, R
2Be hydrogen, methyl, ethyl, methoxyl group or oxyethyl group etc.
2. fluorenone derivatives as claimed in claim 1 is characterized in that, the structural formula of described Fluorenone is:
Described R
1, R
2Hydrogen.
3. fluorenone derivatives as claimed in claim 1 or 2 is characterized in that, it is polysubstituted fluorenone derivatives.
4. such as each described fluorenone derivatives among the claim 1-3, it is characterized in that, it is the efficient synthetic fluorenone derivatives that contains condensed ring.
5. such as the preparation method of fluorenone derivatives as described in the claim 1-4, it is characterized in that, comprise the steps:
Synthesizing of a, substrate;
B, palladium catalysis;
The purifying of c, product.
6. the preparation method of fluorenone derivatives as claimed in claim 5 is characterized in that, step a comprises the steps:
(1) adds methyl alcohol in the adjacent bromoacetophenone as solvent;
(2) NaOH solution is directly poured into and is stirred, and drips phenylacrolein;
(3) drip after, add rinse liquid and reaction;
(4) remove reaction, washing, ethyl acetate extraction, the organic phase anhydrous magnesium sulfate drying is spin-dried for, and the column chromatography for separation crude product gets white solid stand-by;
(5) Pd (PhCN)
2Cl
2Place container with CuI, three take out three fill after, under the condition of inflation, add phenylacetylene and P (t-Bu)
3Skellysolve A solution;
(6) after the stirring, add diisopropylamine, and add rinse liquid;
(7) reinforced complete after, keep the inflated condition reaction;
(8) remove reaction, use ethyl acetate extraction;
(9) boil off solvent, column chromatography separates, and gets faint yellow solid stand-by.
7. such as the preparation method of fluorenone derivatives as described in claim 5 or 6, it is characterized in that, step a comprises:
The 250mL three-necked bottle is contained on the mechanical stirrer, adds 9.95 g(50 mmol in the bottle) adjacent bromoacetophenone, add again 30mL methyl alcohol as solvent; Measure approximately 50mL 15% NaOH solution and directly pour into, stir 2 min after, under the condition of ice-water bath, drip 6.6g(50mmol with constant pressure funnel) phenylacrolein; After dripping, with methyl alcohol rinse dropping funnel, rinse liquid liquid adds in the reaction flask, reacts approximately 3h, removes reaction, washing, ethyl acetate extraction, the organic phase anhydrous magnesium sulfate drying is spin-dried for, the column chromatography for separation crude product gets approximately 14.09 g of white solid, and productive rate 90% is stand-by;
Reaction substrate 1a: weigh 3.13 g (10 mmol) 1.115 mg (0.3 mmol) Pd (PhCN)
2Cl
2Place 50 mL Schlenk bottles with 38 mg (0.2 mmol) CuI, three take out three fill after, under the condition of inflation, add 1.25 g (12 mmol) phenylacetylene and the about P of 2 ml 10% (t-Bu) with syringe
3Skellysolve A solution; Under the condition of ice-water bath, stir half an hour after, add 1.23 g (12 mmol) diisopropylamine, add the syringe Isosorbide-5-Nitrae-dioxane rinse of phenylacetylene and tri-butyl phosphine, rinse liquid adds reactor, after reinforced complete, keep inflated condition reaction 12h; Remove reaction, use ethyl acetate extraction; Boil off solvent, column chromatography separates, and gets faint yellow solid 2.44 g (7.3 mmol), and productive rate 73% is stand-by.
8. such as the preparation method of fluorenone derivatives as described in each among the claim 5-7, it is characterized in that, step b comprises the steps:
In container, add successively reaction substrate 1a, Pd (OAc)
2
Three take out three fills rear adding 3-propargyl bromide, 0.5 mL tri-n-butylamine, DMF;
Be stirred to homogeneous phase under argon gas atmosphere, heat and magnetic agitation to there being palladium black to separate out.
9. the preparation method of fluorenone derivatives as claimed in claim 8, it is characterized in that, step b comprises the steps: in the Schlenk bottle of 25 mL dryings, adds successively 0.334 g (1 mmol) reaction substrate 1a, 4.8 mg (0.02 mmol) Pd (OAc)
2, three take out three fills and adds 0.143 g (1.2 mmol) 3-propargyl bromide with syringe afterwards, 0.5 mL tri-n-butylamine, and 5 mL DMF stir and are heated to 140 ℃ to homogeneous phase under argon gas atmosphere half an hour, and magnetic agitation 18 h are to there being palladium black to separate out.
10. such as the preparation method of fluorenone derivatives as described in each among the claim 5-9, it is characterized in that, step c comprises the steps: stopped reaction, after the question response miscellany is cooled to room temperature, pour in the 15 mL water and extract with ethyl acetate 3 * 10 mL, organic layer is used 15 ml5% dilute hydrochloric acid, 15ml5% yellow soda ash and 15 mL saturated common salt water washings, anhydrous magnesium sulfate drying successively; Filter, vacuum boils off solvent, and crude product separates to get pure compound with column chromatography.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910648A (en) * | 2013-12-30 | 2014-07-09 | 西安万隆制药股份有限公司 | Ubenimex hydrochloride compound |
| CN104370724A (en) * | 2014-12-03 | 2015-02-25 | 安徽师范大学 | Fluorenone derivative, preparation method of fluorenone derivative and redox method of synthetic fluorenone |
-
2013
- 2013-07-10 CN CN201310289772.7A patent/CN103360227B/en active Active
Non-Patent Citations (3)
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| PERUMAL RAJA KUMAR: "A Simple and Versatile Acetylene Equivalent in Diels-Alder Reactions", 《J.CHEM.SOC.,CHEM.COMMUN.》 * |
| 李湖等: "基于钯催化的C-H键选择性官能团化构建C-C键", 《化学进展》 * |
| 沈金海等: "基于钯催化C-H键活化的多米诺反应", 《化学进展》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910648A (en) * | 2013-12-30 | 2014-07-09 | 西安万隆制药股份有限公司 | Ubenimex hydrochloride compound |
| CN103910648B (en) * | 2013-12-30 | 2015-08-26 | 西安万隆制药股份有限公司 | A kind of hydrochloric acid ubenimex compound |
| CN104370724A (en) * | 2014-12-03 | 2015-02-25 | 安徽师范大学 | Fluorenone derivative, preparation method of fluorenone derivative and redox method of synthetic fluorenone |
| CN104370724B (en) * | 2014-12-03 | 2017-01-04 | 安徽师范大学 | A kind of fluorenone derivatives and preparation method thereof, and the oxide-reduction method of synthesis Fluorenone |
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