Spiroalkene derivative and preparation method and application thereof
阅读说明：本技术 一种螺烯衍生物及其制备方法与应用 (Spiroalkene derivative and preparation method and application thereof ) 是由 陈传峰 李猛 于 2020-04-21 设计创作，主要内容包括：本发明公开了一种螺烯衍生物及其制备方法与应用。所述螺烯衍生物的结构式如式Ⅰ-1或式Ⅰ-2所示,式中,Ar为苯基或取代苯基；R为碳原子数为1～5的烷烃或碳原子数为6～12的芳烃。本发明提供的手性螺烯衍生物可用于制备手性有机发光材料,所述有机发光材料具有圆偏振发光性质。本发明提供的制备具有圆偏振发光性质的手性螺烯衍生物的方法,原料廉价,合成方法简单,产物产率高；本发明提供的螺烯衍生物具有消旋能垒高、稳定性好等特点,在手性光电材料领域具有很好的应用前景。(The invention discloses a spiroalkene derivative and a preparation method and application thereof. The structural formula of the spiroalkene derivative is shown as a formula I-1 or a formula I-2, wherein Ar is phenyl or substituted phenyl; r is alkane with 1-5 carbon atoms or arene with 6-12 carbon atoms. The chiral spiroalkene derivative provided by the invention can be used for preparing a chiral organic luminescent material, and the organic luminescent material has a circular polarization luminescent property. The method for preparing the chiral spiroalkene derivative with the circular polarization luminescence property has the advantages of cheap raw materials, simple synthesis method and high product yield; the spiroalkene derivative provided by the invention has the characteristics of high racemization energy barrier, good stability and the like, and has good application prospect in the field of chiral photoelectric materials.)
1. The spiroalkene derivative has a structural formula shown as a formula I-1 or a formula I-2:
in the formula, Ar is phenyl or substituted phenyl;
r is alkane with 1-5 carbon atoms or arene with 6-12 carbon atoms.
2. The spiroalkene derivative of claim 1, wherein: the substituent in the substituted phenyl is alkyl or substituted alkyl with 1-5 carbon atoms, alkoxy with 1-5 carbon atoms, amino or substituted amino, aldehyde group or cyano.
3. The spiroalkene derivative of claim 2, wherein: the substituent in the substituted alkyl is fluorine;
and the substituent in the substituted amino is methyl or phenyl.
4. The spiroalkene derivative of claim 3, wherein: the substituted phenyl is p-trifluoromethylphenyl, p-cyanophenyl, p-aldehyde phenyl, p-dimethylaminophenyl, p-diphenylaminophenyl, p-methylphenyl or p-methoxyphenyl.
5. A process for the preparation of the spiroalkene derivative of any one of claims 1-4 comprising the steps of:
1) reacting a compound of formula A with ArB (OH)2Carrying out reaction to obtain a compound shown as a formula B;
ar is as defined for formula I-1 or formula I-2;
2) reacting the compound shown in the formula B with maleic anhydride to obtain a compound shown in a formula C; reacting the compound shown in the formula C with palladium carbon and sulfur to obtain a compound shown in a formula D;
3) compounds of formula D and RNH2Carrying out reaction to obtain a compound shown as a formula E;
4) chiral resolution of a compound of formula E to obtain an optically pure spiroalkene derivative according to any one of claims 1-4.
6. The method of claim 5, wherein: in the step 1), the reaction is carried out under the catalysis of palladium tetrakis (triphenylphosphine);
a compound of formula A with ArB (OH)2In a molar ratio of 1: 1-5;
the reaction is carried out in a mixed solvent of toluene, ethanol and saturated sodium carbonate aqueous solution;
the reaction temperature is 90-95 ℃, and the reaction time is 6-12 hours.
7. The production method according to claim 5 or 6, characterized in that: in the step 2), the molar ratio of the compound shown as the formula B to the maleic anhydride is 1: 1-5;
the reaction is carried out in xylene;
the reaction is carried out in a reflux state, and the reaction time can be 2-6 hours;
the mass ratio of the compound represented by the formula C to the palladium on carbon and the sulfur is 1: 0.1-0.5: 1-3;
the reaction temperature is 270-300 ℃, and the reaction time is 5-10 minutes.
8. The production method according to any one of claims 5 to 7, characterized in that: in step 3), the compound of formula D and RNH2In a molar ratio of 1: 2-5;
the reaction is carried out in DMF;
the reaction temperature is 90-110 ℃, and the reaction time is 12-24 hours.
9. The production method according to any one of claims 5 to 8, characterized in that: in the step 4), chiral resolution is carried out by utilizing a high performance liquid chromatography chiral column;
the high performance liquid chromatography chiral column isIE semi-preparative column;
the adopted mobile phase is 50: 50 of n-hexane and methane.
10. Use of a spiroalkene derivative according to any one of claims 1 to 4 for the preparation of a chiral organic light emitting material.
11. Use of a spiroalkene derivative according to any one of claims 1 to 4 for the preparation of a circularly polarized electroluminescent material.
Technical Field
The invention relates to a spiroalkene derivative and a preparation method and application thereof, belonging to the field of organic luminescent material chemistry.
Background
Spiroolefins are a class of polycyclic aromatic hydrocarbons with helical chirality derived from aromatic rings by ortho-position fusion. The polycyclic aromatic hydrocarbon has the characteristics of large pi conjugated skeleton and spiral chirality, so that the spiroalkene and the derivative thereof are widely applied to the fields of organic functional materials, asymmetric catalysis, molecular recognition, assembly and the like, and are one of the hot spots of current chemical and material scientific research (chem. Rev.2012,112, 1463-1535). However, the prior spiroalkene compound generally has the problems of low luminous quantum yield, easy chiral racemization and the like, and the synthesis and the derivatization of higher spiroalkene are often limited by the problems of difficult preparation and chiral resolution and the like. Therefore, the design, synthesis and preparation of chiral organic molecules with Circular Polarization Luminescence (CPL) properties by combining the chiral spiroalkene derivatives and the aromatic imide derivatives are new hotspots of research in the field of chiral materials at present, and have high scientific research value and application value.
Disclosure of Invention
The invention aims to provide a spiroalkene derivative, which is a phthalimide spiroalkene derivative substituted by an aromatic ring at the 1, 1' -position, has the properties of high racemization energy barrier, CPL luminescence and the like, can be used for preparing an electroluminescent circular polarization luminescent material, and can be used in the field of chiral photoelectric materials.
The structural formula of the spiroalkene derivative provided by the invention is shown as a formula I-1 or a formula I-2:
in the formula, Ar is phenyl or substituted phenyl;
r is alkane with 1-5 carbon atoms or arene with 6-12 carbon atoms.
Specifically, the substituent in the substituted phenyl is alkyl or substituted alkyl with 1-5 carbon atoms, alkoxy with 1-5 carbon atoms, amino or substituted amino, aldehyde group or cyano;
preferably, the substituents in said substituted alkyl are fluoro;
the substituent in the substituted amino is methyl or phenyl;
the alkyl is preferably an alkyl with 1-3 carbon atoms;
the substituted alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
Preferably, the substituted phenyl group is p-trifluoromethylphenyl, p-cyanophenyl, p-formylphenyl, p-dimethylaminophenyl, p-diphenylaminophenyl, p-methylphenyl or p-methoxyphenyl.
Preferably, R is an aromatic hydrocarbon with 6-12 carbon atoms, and is more preferably a phenyl group.
The invention also provides a preparation method of the spiroalkene derivative, which comprises the following steps:
1) reacting a compound of formula A with ArB (OH)2The reaction is carried out to obtain a compound represented by the formula BA compound;
ar is as defined for formula I-1 or formula I-2;
2) reacting the compound shown in the formula B with maleic anhydride to obtain a compound shown in a formula C; reacting the compound shown in the formula C with palladium carbon and sulfur to obtain a compound shown in a formula D;
3) compounds of formula D and RNH2Carrying out reaction to obtain a compound shown as a formula E;
4) chiral resolution of a compound of formula E to obtain an optically pure spiroalkene derivative according to any one of claims 1-4.
In the preparation method, in the step 1), the reaction is carried out under the catalysis of palladium tetrakis (triphenylphosphine), and the dosage of the catalyst is 1-10 percent, such as 5 percent of the molar weight of the compound shown in the formula A;
a compound of formula A with ArB (OH)2In a molar ratio of 1: 1-5;
the reaction is carried out in a mixed solvent of toluene, ethanol and saturated sodium carbonate aqueous solution, and the volume ratio can be 5: 3: 2;
the reaction temperature is 90-95 ℃, and the reaction time is 6-12 hours.
In the above preparation method, in step 2), the molar ratio of the compound represented by formula B to the maleic anhydride is 1: 1-5;
the reaction is carried out in xylene;
the reaction is carried out in a reflux state, and the reaction time can be 2-10 hours;
the mass ratio of the compound represented by the formula C to the palladium on carbon and the sulfur is 1: 0.1-0.5: 1-3, specifically 1: 0.3: 1;
the reaction temperature is 270-300 ℃, and the reaction time is 5-10 minutes.
In the above preparation method, in step 3), the compound represented by the formula D and RNH2In a molar ratio of 1: 2-5;
the reaction is carried out in DMF;
the reaction temperature is 90-110 ℃, and the reaction time is 12-24 hours.
In the preparation method, in the step 4), chiral resolution is carried out by using a high performance liquid chromatography chiral column;
the high performance liquid chromatography chiral column isIE semi-preparative column;
the adopted mobile phase is 50: 50 of n-hexane and methane.
The chiral spiroalkene derivative provided by the invention can be used for preparing a chiral organic luminescent material, and the organic luminescent material has a circular polarization luminescent property.
The method for preparing the chiral spiroalkene derivative with the circular polarization luminescence property has the advantages of cheap raw materials, simple synthesis method and high product yield; the spiroalkene derivative provided by the invention has the characteristics of high racemization energy barrier, good stability and the like, and has good application prospect in the field of chiral photoelectric materials.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.