CN103435462B - Indenophenanthrylone derivative and preparation method thereof - Google Patents
Indenophenanthrylone derivative and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an indenophenanthrylone derivative and a preparation method thereof. The derivative is a polysubstituted indenophenanthrylone derivative. The preparation method comprises the following steps: a, synthesis of a substrate; b, palladium catalysis; and c, purification of a product. The indenophenanthrylone derivative can be used as a precursor for synthesis and development of a drug; and due to particularity of the structure of the derivative, the indenophenanthrylone derivative may have a certain use value in the field of organic synthesis. The indenophenanthrylone derivative synthesized in the invention has a certain value in theoretical research, so the indenophenanthrylone derivative has wide application prospects in the field of organic synthesis.
Description
Technical field
The present invention relates to a kind of indenes Bing phenanthrenone derivative and preparation method thereof, belong to especially for the synthesis of condensed ring.
Background technology
American Medical according to nineteen ninety-five is reported, the clinical medicine more than 80% on American market comprises at least one ring.And in many natural products, ring texture is also one of its essential condition.In view of the special significance of ring compound, how to go to construct ring texture and cause countless organic synthesis man and chemist actively thinks 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 go to construct ring compound, this kind of method more effectively can synthesize more stable five yuan and six-membered cyclic compound, but paper mill wastewater can affect the carrying out of reaction, and with emulative eliminative reaction, thus the productive rate of reaction is declined, and bring certain trouble to the separation of product.
2) cycloaddition reaction: two or more undersaturated compound forms 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 this kind of reaction, be called dienophile with the alkene of conjugated dienes effect and alkynes.Electron substituent group of giving on electron-withdrawing substituent (as carbonyl, cyano group, nitro, carboxyl etc.) on dienophile and conjugated dienes has the effect that reaction is accelerated.
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, when making reaction different position may occur and obtain two kinds of products, it is main in fact only having a kind of.Thisly reacting by conjugated dienes and alkene or alkynes the reaction generating six-ring, is one of means of very important C―C bond formation in organic chemical synthesis reaction, is also one of reaction conventional in modern organic synthesis.
In addition the cycloaddition reaction be applied also has [2+2] cycloaddition reaction, can be used for synthesizing tetra-atomic ring.
3) diekmann condensation reaction: diester issues in alkali effect the reaction that raw intramolecular condensation generates 'beta '-ketoester.
In this reaction, first the alkali in solution capture the α-hydrogen of ester carbonyl group, Formed negative ion, because carbanion is unstable, will another carbonyl carbon of attack, and addition reaction occurs, and alcoxyl negative ion is left away simultaneously.Alkali captures a α-hydrogen more afterwards, irreversibly generates stable enol negative ion, obtains product finally by acid treatment.
4) Robinson's annulation: react in the presence of a base containing the cyclic ketones of active methylene group and a, b-beta-unsaturated carbonyl compounds, forms the ring system of two and six membered ring:
This reaction is divided into two steps, and the first step is Micheal addition reaction, and second step is aldol reaction.When reacting beginning, there is Michael addition in the enolate nucleophilic attack alpha, beta-unsaturated ketone generated by alkali attack carbonyl compound.The product generated carries out intramolecular aldol condensation immediately under basic conditions, obtains Robinson's annulation product.
5) carbon-hydrogen bond activation of metal catalytic synthesizes monocycle or polynuclear compound
The organic synthesis undertaken by carbon-hydrogen bond activation is development in recent years popular domain rapidly.By the activation of C-H bond, effectively can realize the formation of carbon-carbon bond, thus construct the compound of more complicated.Therefore the direct functionalization reaction of C-H bond is owing to having multiple outstanding advantage and very large challenge, is described as " Holy grail of chemistry ", attracts the concern of more and more scientist.And the method the most effectively realizing carbon-hydrogen bond activation is transition metal-catalyzed cross-coupling reaction.As Suzuki reaction, Heck reacts, Domino reaction etc., after deliberation very ripe at present.And in these cross-coupling reactions, palladium catalyst plays vital effect undoubtedly.As follows for example, just by the catalysis of palladium catalyst, in molecule and intermolecular Heck reaction, realize the carbon-hydrogen bond activation of acetylene bond, a step forms three new carbon-carbon bonds, defines new six-ring compound.Inherently save reactions steps, improve the utilization ratio of atom.
The method of several synthesis of cyclic compounds in sum, due to the existence of ring strain, five yuan and hexa-atomicly more easily to synthesize because its ring strain is less.
Summary of the invention
The object of the present invention is to provide a kind of indenes Bing phenanthrenone derivative and preparation method thereof, can as the precursor in pharmaceutical synthesis and exploitation; And due to the singularity of its structure, it may be made also to have certain utility value in organic synthesis field.
Concrete technical scheme is as follows:
A kind of indenes Bing phenanthrenone derivative, its structural formula is:
Described R
1for hydrogen or fluorine, R2, R3 are hydrogen, methyl or ethyl etc.
Further, the structural formula of described indenes Bing phenanthrenone is:
Described R
1hydrogen, R
2, R
3it is methyl.
Further, it is polysubstituted indenes Bing phenanthrenone derivative.
Further, it is the indenes Bing phenanthrenone derivative of efficient synthesis containing condensed ring.
The preparation method of above-mentioned indenes Bing phenanthrenone derivative, comprises the steps:
The synthesis of a, substrate;
B, palladium chtalyst;
The purifying of c, product.
Further, step a comprises the steps:
(1) synthesis of 2-bromine cinnamophenone: adjacent bromoacetophenone and NaOH solution are directly poured in container successively;
(2) add methanol as solvent and stir;
(3) naphthaldehyde after methanol dilution is dripped;
(4) after dripping reaction, remove reaction unit, washing, is extracted with ethyl acetate, and organic phase anhydrous magnesium sulfate drying leaves standstill, and is spin-dried for, adds silica gel and drain, being separated crude product with column chromatography, obtaining white solid stand-by after filtration with Rotary Evaporators;
(5) by the synthesis of substrate 1a: by 2-bromine cinnamophenone, Pd (PhCN)
2cl
2join successively in container with CuI;
(6) three take out three fill after, add the 2-methyl-3-butyne-2-alcohol with the dilution of Isosorbide-5-Nitrae-dioxane and P (t-Bu) 3 Skellysolve A solution successively;
(7), after stirring 30min, add diisopropylamine and react;
(8) remove reaction unit, washing, extraction into ethyl acetate, organic phase anhydrous magnesium sulfate drying leaves standstill a night, is spin-dried for, adds silica gel and drain, being separated crude product with column chromatography, obtaining faint yellow solid stand-by after filtration with Rotary Evaporators.
Further, step a comprises:
The synthesis of 2-bromine cinnamophenone: three-necked bottle 250mL being contained magneton is fixed on magnetic stirring apparatus, the adjacent bromoacetophenone of 50mmol and about 60mL15%NaOH solution are directly poured in bottle successively, then the methanol as solvent of about 70mL is added, after stirring 15min, under the condition of ice-water bath, the naphthaldehyde constant pressure funnel of the 50mmol after methanol dilution is dripped, after dripping reaction 3h, remove reaction unit, washing, be extracted with ethyl acetate, organic phase anhydrous magnesium sulfate drying leaves standstill 3h, be spin-dried for Rotary Evaporators after filtration, add silica gel and drain, crude product is separated with column chromatography, obtain white solid stand-by,
Synthesis by substrate 1a: by 10mmol2-bromine cinnamophenone, 115mg (0.3mmol) Pd (PhCN)
2cl
2join in the Schlenk bottle of 50mL drying successively with 38mg (0.2mmol) CuI, under the condition of argon shield, three take out three fill after, add with about 15mL1 successively with syringe, 12mmol2-methyl-3-the butyne-2-alcohol of 4-dioxane dilution and P (t-Bu) the 3 Skellysolve A solution of about 2ml10%, after stirring 30min, under the condition of ice-water bath, add 12mmol diisopropylamine, reaction 12h; Remove reaction unit, washing, extraction into ethyl acetate, organic phase anhydrous magnesium sulfate drying leaves standstill a night, is spin-dried for, adds silica gel and drain, being separated crude product with column chromatography, obtaining faint yellow solid stand-by after filtration with Rotary Evaporators.
Further, step b comprises the steps:
By reaction substrate 1a and Pd (OAc)
2join successively in container;
Three take out three fills rear syringe and adds 3-propargyl bromide successively, (n-Bu) 3N and DMF;
Heating magnetic agitation reflux, stop reaction and remove reaction unit after being cooled to room.
Further, step b comprises the steps: 1mmol reaction substrate 1a and 4.8mg (0.02mmol) Pd (OAc)
2join in the Schlenk bottle of 25mL drying successively; three take out three fills rear syringe and adds 0.143g (1.2mmol) 3-propargyl bromide successively; 0.5mL (n-Bu) 3N and 5mLDMF; 140 DEG C are heated under argon shield; magnetic agitation reflux 18h, stops reaction and removes reaction unit after being cooled to room.
Further, step c comprises the steps: mixed solution to pour in separating funnel and adds 15mL water and use 10mL extraction into ethyl acetate three times, then by rare for organic layer 15ml5% HCl, 15ml5%Na
2cO
3wash successively with 15mL saturated aqueous common salt, use anhydrous MgSO
4at a dry standing night, filter, add silica gel after being spin-dried for Rotary Evaporators and drain stand-by, crude product column chromatography is separated to obtain pure compound.
The present invention compared with prior art, provides a kind of synthetic method of brand-new fused ring compound, generates a series of new indeno phenanthrenone derivative.From producing or the angle of theory, ketone all occupies extremely important status, many ketones are important industrial raw material, produce with very huge quantity, some is spices or important product, and the indeno phenanthrenone derivative therefore synthesized by the present invention still has certain purposes in real life.
Chemically in performance and at various synthetic use, ketone all occupies special critical positions, and often they are beginning raw materials of synthesis.Synthetic work person has a kind of like this understanding, be exactly had a ketone group or aldehyde radical in the molecule, this molecule just becomes has lived, molecule is just provided with easily by the position of attack, starting point is made with this position, carry out next step reaction, the indeno phenanthrenone derivative therefore synthesized by the present invention also has certain value in theoretical investigation.The application prospect of indeno phenanthrenone derivative in organic synthesis field still very widely thus.
Accompanying drawing explanation
Fig. 1 a, Fig. 1 b, Fig. 1 c, Fig. 1 d are indenes Bing phenanthrenone derivant structure formula of the present invention
Fig. 2 a, Fig. 2 b, Fig. 2 c, Fig. 2 d is the proton nmr spectra of the embodiment of the present invention
Embodiment
Describe the present invention with reference to the accompanying drawings below, it is a kind of preferred embodiment in numerous embodiments of the present invention.
A kind of indenes Bing phenanthrenone derivative, described its structural formula of indenes Bing phenanthrenone derivative is:
Described R
1for hydrogen, fluorine, R2, R3 are hydrogen, methyl, ethyl etc.
The structural formula of preferred indenes Bing phenanthrenone is:
Namely described R
1hydrogen R
2, R
3it is methyl
Preparation method of the present invention is: the purifying of the synthesis of a, substrate, b, palladium chtalyst, c, product.
Synthesizing of described a, substrate:
The synthesis of substrate is in two steps: one is the synthesis of 2-bromine cinnamophenone, three-necked bottle 250mL being contained magneton is fixed on magnetic stirring apparatus, the adjacent bromoacetophenone of 50mmol and about 60mL15%NaOH solution are directly poured in bottle successively, then the methanol as solvent of about 70mL is added, after stirring 15min, under the condition of ice-water bath, the naphthaldehyde constant pressure funnel of the 50mmol after methanol dilution is dripped, after dripping reaction 3h, remove reaction unit, washing, be extracted with ethyl acetate, organic phase anhydrous magnesium sulfate drying leaves standstill 3h, be spin-dried for Rotary Evaporators after filtration, add silica gel and drain, crude product (EA:PE=1:30) is separated with column chromatography, obtain white solid stand-by.Two is by the synthesis of substrate 1a, by 10mmol2-bromine cinnamophenone, 115mg (0.3mmol) Pd (PhCN)
2cl
2join in the Schlenk bottle of 50mL drying successively with 38mg (0.2mmol) CuI; under the condition of argon shield; three take out three fill after; P (t-Bu) the 3 Skellysolve A solution of 12mmol2-methyl-3-butyne-2-alcohol and the about 2ml10% diluted with Isosorbide-5-Nitrae-dioxane (about 15mL) is added successively with syringe.After stirring 30min, under the condition of ice-water bath, add 12mmol diisopropylamine, reaction 12h.Remove reaction unit, washing, extraction into ethyl acetate, organic phase anhydrous magnesium sulfate drying leaves standstill a night, is spin-dried for, adds silica gel and drain after filtration with Rotary Evaporators, be separated crude product (EA:PE=1:20) with column chromatography, obtain faint yellow solid stand-by.
Described b, palladium chtalyst are:
1mmol reaction substrate 1a and 4.8mg (0.02mmol) Pd (OAc) 2 is joined in the Schlenk bottle of 25mL drying successively, three take out three fills rear syringe and adds 0.143g (1.2mmol) 3-propargyl bromide successively, 0.5mL (n-Bu) 3N and 5mLDMF.Under argon shield, be heated to 140 DEG C, magnetic agitation reflux 18h, reaction stopped and removing reaction unit after being cooled to room.
The purifying of described c, product is:
Mixed solution is poured in separating funnel and add 15mL water and use 10mL extraction into ethyl acetate three times, then by rare for organic layer 15ml HCl (5%), 15mlNa
2cO
3(5%) and 15mL saturated aqueous common salt wash successively, leave standstill a night with anhydrous MgSO4 drying.Filter, add silica gel after being spin-dried for Rotary Evaporators and drain stand-by, crude product column chromatography is separated to obtain pure compound (EA/PE=1:4).
In another preferred embodiment, the synthesis of indenes Bing phenanthrenone 3a:
Shown in synthetic route.
The synthesis of a, substrate:
The synthesis of substrate is in two steps: one is the synthesis of 2-bromine cinnamophenone, three-necked bottle 250mL being contained magneton is fixed on magnetic stirring apparatus, the adjacent bromoacetophenone of 50mmol and about 60mL15%NaOH solution are directly poured in bottle successively, then the methanol as solvent of about 70mL is added, after stirring 15min, under the condition of ice-water bath, the naphthaldehyde constant pressure funnel of the 50mmol after methanol dilution is dripped, after dripping reaction 3h, remove reaction unit, washing, be extracted with ethyl acetate, organic phase anhydrous magnesium sulfate drying leaves standstill 3h, be spin-dried for Rotary Evaporators after filtration, add silica gel and drain, crude product (EA:PE=1:30) is separated with column chromatography, obtain white solid stand-by.Two is by the synthesis of substrate 1a, by 10mmol2-bromine cinnamophenone, 115mg (0.3mmol) Pd (PhCN)
2cl
2join in the Schlenk bottle of 50mL drying successively with 38mg (0.2mmol) CuI; under the condition of argon shield; three take out three fill after; P (t-Bu) the 3 Skellysolve A solution of 12mmol2-methyl-3-butyne-2-alcohol and the about 2ml10% diluted with Isosorbide-5-Nitrae-dioxane (about 15mL) is added successively with syringe.After stirring 30min, under the condition of ice-water bath, add 12mmol diisopropylamine, reaction 12h.Remove reaction unit, washing, extraction into ethyl acetate, organic phase anhydrous magnesium sulfate drying leaves standstill a night, is spin-dried for, adds silica gel and drain after filtration with Rotary Evaporators, be separated crude product (EA:PE=1:20) with column chromatography, obtain faint yellow solid stand-by.
B, palladium chtalyst
By 1mmol reaction substrate 1a and 4.8mg (0.02mmol) Pd (OAc)
2join in the Schlenk bottle of 25mL drying successively, three take out three fills rear syringe and adds 0.143g (1.2mmol) 3-propargyl bromide successively, 0.5mL (n-Bu) 3N and 5mLDMF.Under argon shield, be heated to 140 DEG C, magnetic agitation reflux 18h, reaction stopped and removing reaction unit after being cooled to room.
The purifying of c, product
Mixed solution is poured in separating funnel and add 15mL water and use 10mL extraction into ethyl acetate three times, then by rare for organic layer 15ml HCl (5%), 15mlNa
2cO
3(5%) and 15mL saturated aqueous common salt wash successively, use anhydrous MgSO
4a dry standing night.Filter, add silica gel after being spin-dried for Rotary Evaporators and drain stand-by, crude product column chromatography is separated to obtain pure compound (EA/PE=1:4).
The structure of indeno phenanthrenone 3a is passed through;
1hNMR;
13cNMR; HRMS; IR measures.
Indenes Bing phenanthrenone 3a:1HNMR (300MHz, CDCl
3): δ 8.24 (s, 1H), 7.75-7.86 (m, 4H); 7.69-7.70 (m, 1H), 7.40-7.52 (m; 1H), 7.36 (d, J=8.7Hz; 2H), 7.17-7.26 (m, 3H); 6.76-6.90 (m, 1H), 5.63-5.66 (m; 1H), 4.02 (s, 3H);
13cNMR (75MHz, CDCl
3): δ 191.68,166.82 (d, J
c-F=252.1Hz), 159.94,148.71,148.57,138.07; 136.33,134.92,134.18,133.09,132.45; 131.38,130.02,129.19,129.06; 128.59,127.89,127.05,125.96; 125.86,125.29,115.92,115.32; 115.01,112.29,111.93,55.56ppm;
FT-IR(KBr):ν1715,1609,1510,1454,1232,1175,1028,764cm-1;
HRMS(EI):m/z[M]+calcd for C28H17O2F:404.1213;found:404.1211.
Above by reference to the accompanying drawings to invention has been exemplary description; obvious specific implementation of the present invention is not subject to the restrictions described above; as long as have employed the various improvement that method of the present invention is conceived and technical scheme is carried out; or directly apply to other occasion, all within protection scope of the present invention without improving.
Claims (4)
1. a preparation method for indenes Bing phenanthrenone derivative, is characterized in that, the structural formula of indenes Bing phenanthrenone derivative is:
Described R
1for hydrogen or fluorine, R2, R3 are hydrogen, methyl or ethyl; Comprise the steps:
The synthesis of a, substrate:
(1) synthesis of 2-bromine cinnamophenone: adjacent bromoacetophenone and NaOH solution are directly poured in container successively;
(2) add methanol as solvent and stir;
(3) naphthaldehyde after methanol dilution is dripped;
(4) after dripping reaction, remove reaction unit, washing, is extracted with ethyl acetate, and organic phase anhydrous magnesium sulfate drying leaves standstill, and is spin-dried for, adds silica gel and drain, being separated crude product with column chromatography, obtaining white solid stand-by after filtration with Rotary Evaporators;
(5) synthesis of substrate 1a: by 2-bromine cinnamophenone, Pd (PhCN)
2cl
2join successively in container with CuI;
(6) three take out three fill after, add the 2-methyl-3-butyne-2-alcohol with the dilution of Isosorbide-5-Nitrae-dioxane and P (t-Bu) 3 Skellysolve A solution successively;
(7), after stirring 30min, add diisopropylamine and react;
(8) remove reaction unit, washing, extraction into ethyl acetate, organic phase anhydrous magnesium sulfate drying leaves standstill a night, is spin-dried for, adds silica gel and drain, being separated crude product with column chromatography, obtaining faint yellow solid stand-by after filtration with Rotary Evaporators;
B, palladium chtalyst:
By reaction substrate 1a and Pd (OAc)
2join successively in container;
Three take out three fills rear syringe and adds 3-propargyl bromide successively, (n-Bu) 3N and DMF;
Heating magnetic agitation reflux, stop reaction and remove reaction unit after being cooled to room;
The purifying of c, product:
Mixed solution is poured in separating funnel and add 15mL water and use 10mL extraction into ethyl acetate three times, then by rare for organic layer 15ml5% HCl, 15ml5%Na
2cO
3wash successively with 15mL saturated aqueous common salt, use anhydrous MgSO
4at a dry standing night, filter, add silica gel after being spin-dried for Rotary Evaporators and drain stand-by, crude product column chromatography is separated to obtain pure compound.
2. the preparation method of indenes Bing phenanthrenone derivative as claimed in claim 1, it is characterized in that, the structural formula of described indenes Bing phenanthrenone is:
Described R
1hydrogen, R
2, R
3it is methyl.
3. the preparation method of indenes Bing phenanthrenone derivative as claimed in claim 1, it is characterized in that, step a comprises:
The synthesis of 2-bromine cinnamophenone: three-necked bottle 250mL being contained magneton is fixed on magnetic stirring apparatus, the adjacent bromoacetophenone of 50mmol and 60mL15%NaOH solution are directly poured in bottle successively, then the methanol as solvent of 70mL is added, after stirring 15min, under the condition of ice-water bath, the naphthaldehyde constant pressure funnel of the 50mmol after methanol dilution is dripped, after dripping reaction 3h, remove reaction unit, washing, be extracted with ethyl acetate, organic phase anhydrous magnesium sulfate drying leaves standstill 3h, be spin-dried for Rotary Evaporators after filtration, add silica gel and drain, crude product is separated with column chromatography, obtain white solid stand-by,
The synthesis of substrate 1a: by 10mmol2-bromine cinnamophenone, 115mg (0.3mmol) Pd (PhCN)
2cl
2join in the Schlenk bottle of 50mL drying successively with 38mg (0.2mmol) CuI, under the condition of argon shield, three take out three fill after, add with 15mL1 successively with syringe, 12mmol2-methyl-3-the butyne-2-alcohol of 4-dioxane dilution and P (t-Bu) the 3 Skellysolve A solution of 2ml10%, after stirring 30min, under the condition of ice-water bath, add 12mmol diisopropylamine, reaction 12h; Remove reaction unit, washing, extraction into ethyl acetate, organic phase anhydrous magnesium sulfate drying leaves standstill a night, is spin-dried for, adds silica gel and drain, being separated crude product with column chromatography, obtaining faint yellow solid stand-by after filtration with Rotary Evaporators.
4. the preparation method of indenes Bing phenanthrenone derivative as claimed in claim 1, it is characterized in that, step b comprises the steps: 1mmol reaction substrate 1a and 4.8mg (0.02mmol) Pd (OAc)
2join in the Schlenk bottle of 25mL drying successively; three take out three fills rear syringe and adds 0.143g (1.2mmol) 3-propargyl bromide successively; 0.5mL (n-Bu) 3N and 5mLDMF; 140 DEG C are heated under argon shield; magnetic agitation reflux 18h, stops reaction and removes reaction unit after being cooled to room.
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| CN106749280B (en) * | 2017-01-16 | 2018-09-18 | 河南师范大学 | 5H- quinazolines [3,2-b] cinnolines -7,13- cyclohexadione compounds and preparation method thereof |
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| EP0363128A2 (en) * | 1988-09-30 | 1990-04-11 | Arch Development Corporation | Anti-androgen compounds |
| US6310256B1 (en) * | 1999-03-03 | 2001-10-30 | The Dow Chemical Company | Synthesis of 4-ketocyclopentene compounds |
| CN102040589A (en) * | 2009-10-09 | 2011-05-04 | 三星移动显示器株式会社 | Condensed-cyclic compound and organic light emitting diode |
| CN102603685A (en) * | 2011-01-19 | 2012-07-25 | 中国药科大学 | Flavonoid fatty acid ester derivatives, preparation method and medicinal use of flavonoid fatty acid ester derivatives |
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| EP0363128A2 (en) * | 1988-09-30 | 1990-04-11 | Arch Development Corporation | Anti-androgen compounds |
| US6310256B1 (en) * | 1999-03-03 | 2001-10-30 | The Dow Chemical Company | Synthesis of 4-ketocyclopentene compounds |
| CN102040589A (en) * | 2009-10-09 | 2011-05-04 | 三星移动显示器株式会社 | Condensed-cyclic compound and organic light emitting diode |
| CN102603685A (en) * | 2011-01-19 | 2012-07-25 | 中国药科大学 | Flavonoid fatty acid ester derivatives, preparation method and medicinal use of flavonoid fatty acid ester derivatives |
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