CN107954821A - A kind of ruthenium catalysis dibenzyl ketone prepares method and the application of more virtue substitution naphthalene derivativeses with interior alkynes cyclization - Google Patents
A kind of ruthenium catalysis dibenzyl ketone prepares method and the application of more virtue substitution naphthalene derivativeses with interior alkynes cyclization Download PDFInfo
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Abstract
Method and the application of more virtue substitution naphthalene derivativeses are prepared with interior alkynes cyclization the present invention relates to a kind of ruthenium catalysis dibenzyl ketone.The present invention uses more cheap ruthenium ([RuCl2(p‑cymene)]2) catalyst is used as, dibenzyl ketone β H are activated synthesis hexatomic ring generates more virtue substitution naphthalene derivativeses；Without additive and oxidant in reaction process, using only simple alkali, carry out under mild reaction conditions.Synthetic method provided by the invention is simple and practicable, scientific and reasonable, environmentally protective, economical and practical, is adapted to large-scale production.
Description
Technical field
The present invention relates to medical science and field of photovoltaic materials, relate generally to more virtue substitution naphthalene derivativeses preparation method and
Using.
Background technology
More virtue substitution naphthalene derivativeses are due to its unique electrochemistry, photochemical properties and the function material that they are conjugated in n
Application on material, makes it more and more extensive in the application of organic fluorescence materials, semi-conducting material etc., and more virtue substitution naphthalenes
Derivative also has important application in terms of pharmaceutical synthesis.The preparation method used in the prior art compares pervious ring metal
Change, aryl halide, aryl acid etc. have very big breakthrough than relatively severe condition.At present, use passed through more in a mild condition
Cross c h bond (or even the double c h bonds) activation of metal catalytic fragrance phenyl ring and the naphthalene that cyclization prepares more virtue substitutions occurs for alkynes
Derivative.But this method existing defects, these reactions need the metal salt of a certain amount of ligand or equivalent to do oxidant ability
Catalytic cycle is completed, not only increases production cost, and metal salt is mostly heavy metal (copper, silver etc.) salt of environmental pollution
Class.Based on this, this area needs more environmentally-friendly, green, economic method to synthesize more virtue substitution naphthalene derivativeses.
The content of the invention
To make up the deficiencies in the prior art, the present invention provides one kind without additive and oxidant in a mild condition with
More cheap ruthenium ([RuCl2(p-cymene)]2) as catalyst synthesized it is more virtue substitution naphthalene derivatives methods.
The present invention adopts the following technical scheme that：More virtue substitution naphthalene derivatives, have the structure as shown in general formula I：
Another object of the present invention is that the preparation method of above-mentioned more virtue substitution naphthalene derivatives is claimed, i.e.,：By dibenzyl
Base ketone and interior alkynesAs raw material, [RuCl is added2(p-cymene)]2, alkali and non-polar organic solvent, in nitrogen
80-100 DEG C of reaction 12-24h is heated under compression ring border, more virtue substitution naphthalene derivatives are obtained through column chromatography for separation；Described is interior
Alkynes is 1 with dibenzyl ketone molar ratio:2, [RuCl2(p-cymene)]2Account for the 15mol% of interior alkynes, alkali and dibenzyl ketone rub
You are than being 1:1.
Further, the non-polar organic solvent for benzene, toluene, dichloroethanes, chloroform, styrene, cyclohexane or oneself
It is any in alkane.It is preferred that toluene.
Further, the alkali is KOAc, Na2CO3、Cs2CO3、K2CO3、Li2CO3, one kind in NaOAc, LiOAc or
More than one.It is preferred that KOAc and Na2CO3。
As the preferred embodiment of the invention, the preparation method of more virtue substitution naphthalene derivativeses is：By dibenzyl ketone
It is placed in interior alkynes in tube sealing, adds [RuCl2(p-cymene)]2And toluene, while dry sodium carbonate and potassium acetate are added in nitrogen
Be heated under compression ring border 100 DEG C of reactions 24 it is small when, obtain more virtue substitution naphthalene derivatives through column chromatography for separation.
3rd purpose of the invention is that above-mentioned more virtue substitution naphthalene derivatives are claimed in medicine preparation and photoelectric material
Application on field.
For example it is used for Novel tyrosine protein kinase inhibitorOr blue light material
Preparation.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention uses more cheap ruthenium ([RuCl2(p-cymene)]2) catalyst is used as, dibenzyl ketone β-H are activated
Synthesize hexatomic ring and generate more virtue substitution naphthalene derivativeses；Without additive and oxidant in reaction process, using only simple alkali,
Carry out under mild reaction conditions.Synthetic method provided by the invention is simple and practicable, scientific and reasonable, environmentally protective, economical and practical,
It is adapted to large-scale production.
Embodiment
The present invention is described in detail below by specific embodiment, but is not limited the scope of the invention.Unless otherwise specified, originally
Experimental method is conventional method used by invention, and experiment equipment used, material, reagent etc. can chemically company be bought.
Embodiment 1
Dibenzyl ketone (42mg, 0.2mmol), corresponding interior alkynes are added into the 25mL tube sealings with magneton
(0.1mmol), catalyst [RuCl2(p-cymene)]2(9mg, 15%mol), 0.5mL toluene, adds dry sodium carbonate afterwards
(21mg, 0.2mmol), potassium acetate (19mg, 0.2mmol), substitutes nitrogen three times, when reaction 24 is small at 100 DEG C, then through column color
(eluant, eluent is for spectrum separation：Petroleum ether) so as to obtain target compound.It is characterized as below.
3- benzyl -1- methyl -2- phenylnaphthalenes：Yield：40%.Fusing point：76-77℃.1H NMR(CDCl3,400MHz)δ
8.03 (d, J=8.0Hz, 1H), 7.79 (d, J=8.0Hz, 1H), 7.47-7.52 (m, 3H), 7.33-7.36 (m, 3H), 7.12-
7.17 (m, 3H), 7.03-7.05 (m, 2H), 6.88 (d, J=6.8Hz, 2H), 3.83 (s, 2H), 2.36 (s, 3H)13C NMR
(CDCl3,100MHz)δ141.0,140.9,140.1,137.4,132.8,132.1,129.7,129.1,128.2,128.1,
128.1,126.7,126.5,125.7,125.6,125.6,124.4,40.8,16.6.HRMS(EI-TOF)calcd for
C24H20(M+):308.1565,found:308.1563.
Comparative example：Tolans 0.1mmol, aromatic ketone are added into the 25mL tube sealings with magneton
(0.2mmol), catalyst [RuCl2(p-cymene)]20.01mol, adds 0.5mL organic solvents and rubs with aromatic ketone etc. afterwards
The alkali of your drying, substitutes nitrogen three times, reacted at 100 DEG C 24 it is small when, then through pillar layer separation, (eluant, eluent is：Petroleum ether)
So as to obtain target compoundYield is calculated, the results are shown in Table 1.
Table 1
| Sequence number | Alkali | Organic solvent | Yield |
| 1 | KOAc | PhMe | 0 |
| 2 | LiOAc | PhMe | 0 |
| 3 | NaOAc | PhMe | Seldom |
| 4 | CsOAc | PhMe | 20 |
| 5 | Li2CO3 | PhMe | Seldom |
| 6 | Na2CO3 | PhMe | Seldom |
| 7 | K2CO3 | PhMe | 25 |
| 8 | Cs2CO3 | PhMe | 23 |
| 9 | KOAc, Na2CO3 | PhMe | 52 |
| 10 | KOAc, Na2CO3 | DCE | 23 |
| 11 | KOAc, Na2CO3 | PhF | 21 |
| 12 | KOAc, Na2CO3 | CH3CN | 0 |
| 13 | KOAc, Na2CO3 | DMSO | 0 |
| 14 | KOAc, Na2CO3 | PhMe | 70%* |
* yield when catalyst is 0.015mmol
Contrasted from 1 data of table and to 1 yield of embodiment, when organic solvent selects toluene, alkali is sodium carbonate and acetic acid
During potassium, when catalyst amount is 15mol%, yield highest.So in experimentation using this optimum reaction condition into
OK.
The above, is only the preferable embodiment of the invention, but the protection domain of the invention is not
This is confined to, any one skilled in the art is in the technical scope that the invention discloses, according to the present invention
The technical solution of creation and its inventive concept are subject to equivalent substitution or change, should all cover the invention protection domain it
It is interior.
Claims (8)
1. a kind of more virtue substitution naphthalene derivatives, it is characterised in that there is the structure as shown in general formula I：
A kind of 2. preparation methods of virtue substitution naphthalene derivativeses more as claimed in claim 1, it is characterised in that by dibenzyl ketone with
Interior alkynesAs raw material, [RuCl is added2(p-cymene)]2, alkali and non-polar organic solvent, in a nitrogen environment
80-100 DEG C of reaction 12-24h is heated to, more virtue substitution naphthalene derivatives are obtained through column chromatography for separation；The interior alkynes and dibenzyl
Base ketone molar ratio is 1:2, [RuCl2(p-cymene)]2Account for the 15mol% of interior alkynes, the molar ratio of alkali and dibenzyl ketone is 1:1.
3. according to the method described in claim 2, it is characterized in that, the non-polar organic solvent is benzene, toluene, two chloroethenes
It is any in alkane, chloroform, styrene, cyclohexane or hexane.
4. according to the method described in claim 3, it is characterized in that, organic solvent is toluene.
5. according to the method described in claim 2, it is characterized in that, the alkali is KOAc, Na2CO3、Cs2CO3、K2CO3、
Li2CO3, one or more in NaOAc, LiOAc.
6. according to the method described in claim 5, it is characterized in that, the alkali is KOAc and Na2CO3。
7. according to the method described in claim 2, it is characterized in that, the preparation method of more virtue substitution naphthalene derivativeses is：By two
Benzyl ketone withIt is placed in tube sealing, adds [RuCl2(p-cymene)]2And toluene, while add dry carbonic acid
Sodium and potassium acetate be heated in a nitrogen environment 100 DEG C of reactions 24 it is small when, obtain the derivatives of more virtue substitution naphthalenes through column chromatography for separation
Thing；
DescribedIt is 1 with dibenzyl ketone molar ratio:2, [RuCl2(p-cymene)]2The 15mol% of interior alkynes is accounted for,
The molar ratio of alkali and dibenzyl ketone is 1:1.
A kind of 8. application of more virtue substitution naphthalene derivativeses as claimed in claim 1 in medicine preparation and field of photovoltaic materials.
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| CN201711329750.3A CN107954821B (en) | 2017-12-13 | 2017-12-13 | Method for preparing polyaromatic substituted naphthalene derivative by cyclization reaction of ruthenium-catalyzed dibenzyl ketone and internal alkyne and application |
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| CN201711329750.3A CN107954821B (en) | 2017-12-13 | 2017-12-13 | Method for preparing polyaromatic substituted naphthalene derivative by cyclization reaction of ruthenium-catalyzed dibenzyl ketone and internal alkyne and application |
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| CN107954821A true CN107954821A (en) | 2018-04-24 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426457A (en) * | 2021-12-27 | 2022-05-03 | 玉林师范学院 | Method for preparing naphthalene derivative and application |
| CN114426533A (en) * | 2021-12-23 | 2022-05-03 | 玉林师范学院 | Method for preparing polyaryl substituted benzothiophene through ruthenium catalysis and application |
| CN114478208A (en) * | 2021-12-27 | 2022-05-13 | 玉林师范学院 | Polyarylnaphthalene derivative and preparation method and application thereof |
| CN114478158A (en) * | 2021-12-27 | 2022-05-13 | 玉林师范学院 | Application of polysubstituted naphthalene derivative |
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| CN101624322A (en) * | 2009-08-05 | 2010-01-13 | 苏州大学 | Method for preparing 1, 2-diketone by catalyzing and oxidizing alkynes |
| WO2012156591A1 (en) * | 2011-05-19 | 2012-11-22 | IFP Energies Nouvelles | Ruthnium-based catalytic composition including a silane or siloxane compound and method for methasizing olefins using said composition |
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Patent Citations (2)
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| CN101624322A (en) * | 2009-08-05 | 2010-01-13 | 苏州大学 | Method for preparing 1, 2-diketone by catalyzing and oxidizing alkynes |
| WO2012156591A1 (en) * | 2011-05-19 | 2012-11-22 | IFP Energies Nouvelles | Ruthnium-based catalytic composition including a silane or siloxane compound and method for methasizing olefins using said composition |
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| RAVI KIRAN CHINNAGOLLA ET AL.: "Ruthenium-Catalyzed Regioselective Cyclization of Aromatic Ketones with Alkynes: An Efficient Route to Indenols and Benzofulvenes", 《EUR. J. ORG. CHEM.》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426533A (en) * | 2021-12-23 | 2022-05-03 | 玉林师范学院 | Method for preparing polyaryl substituted benzothiophene through ruthenium catalysis and application |
| CN114426457A (en) * | 2021-12-27 | 2022-05-03 | 玉林师范学院 | Method for preparing naphthalene derivative and application |
| CN114478208A (en) * | 2021-12-27 | 2022-05-13 | 玉林师范学院 | Polyarylnaphthalene derivative and preparation method and application thereof |
| CN114478158A (en) * | 2021-12-27 | 2022-05-13 | 玉林师范学院 | Application of polysubstituted naphthalene derivative |
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