CN108409765B - Nopinanyl beta-diketone boron difluoride complex and preparation method and application thereof - Google Patents
Nopinanyl beta-diketone boron difluoride complex and preparation method and application thereof Download PDFInfo
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- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
Abstract
The invention discloses a nopinyl beta-diketone boron difluoride complex and a synthesis method and application thereof. The invention uses the oxidation product nopinone of natural renewable resource beta-pinene as raw material to prepare novel nopinonyl beta-diketone boron difluoride complexes 3a and 3 b. Performing claisen condensation reaction on nopinone, methyl p-methoxybenzoate 1a and methyl p-bromobenzoate 1b to respectively prepare nopinone alkyl beta-diketone compounds 2a and 2 b; the compounds 2a and 2b are then complexed with boron trifluoride ethyl ether to respectively prepare nopinyl beta-diketone boron difluoride complexes 3a and 3 b. The nopinyl beta-diketone boron difluoride complexes 3a and 3b have good fluorescence properties and high fluorescence quantum yield, and when the nopinyl beta-diketone boron difluoride complexes are used as luminescent materials to be applied to electroluminescent devices, the devices emit blue-green light. The nopaline beta-diketone boron difluoride complex is shown to have good application value in the preparation of electroluminescent devices as a luminescent material.
Description
Technical Field
The invention belongs to the technical field of fine organic synthesis and the technical field of synthesis of novel electroluminescent materials, and relates to a nopinonyl beta-diketone boron difluoride complex and a preparation method and application thereof.
Background
the beta-diketone boron fluoride compound has a plurality of optical and structural advantages as an important fluorescent dye, such as high fluorescence quantum yield, high electron mobility, large molar absorption coefficient and the like, so that the beta-diketone boron fluoride compound is widely applied to the fields of molecular probes, optical imaging, solar cells, laser dyes, gel and the like, and the synthesis of the compound has the advantages of simple process, high yield, easy purification and the like, so the beta-diketone boron fluoride compound is concerned by the majority of scientific researchers. A large number of researches show that the complete BF2 is a basic unit of the beta-diketone boron fluoride compound, and the change of the structure of aldehyde ester has a remarkable influence on the optical performance of the aldehyde ester.
nopinone is a derivative of beta-pinene, and beta-pinene is one of the main components of turpentine oil, a natural resource. Nopinone has carbonyl group, can carry out various reactions such as substitution, oxidation, reduction, isomerization and the like, has higher reaction activity, and is an ideal raw material for synthesizing products with high added value. The nopinone is utilized to synthesize a plurality of new compounds, such as p-isopropylphenol, triazolone compounds, chiral 1, 3-aminoethanol and the like, and has practical application value in the industries of fine chemical engineering, medical food, materials and the like.
In recent years, compounds such as tetraphenylethylenes, siloles, tetraphenyl-1, 4-butadiene, 6, 13-pentabenzoquinone, boron fluoride dipyrrole and the like are widely used in electroluminescent materials, but no reports have been made about the synthesis of compounds for electroluminescent materials using natural products as raw materials.
Disclosure of Invention
the purpose of the invention is as follows: aiming at the defects in the prior art, the invention aims to provide a nopinyl beta-diketone boron difluoride complex which meets the use requirement of a luminescent material. The invention also aims to provide a synthesis method of the nopinyl beta-diketone boron difluoride complex. The invention also aims to provide application of the compound as a luminescent material in an electroluminescent device.
the technical scheme is as follows: in order to achieve the purpose of the invention, the invention adopts the technical scheme that:
The nopinyl beta-diketone boron difluoride complex has a structural formula as follows:
In the formula: r is OCH3 and Br.
the specific name and structural formula of the nopaline beta-diketone boron difluoride complex are as follows:
Compound 3 a: 2, 2-difluoro-4- (4-methoxyphenyl) -7, 7-dimethyl-5, 6,7, 8-tetrahydro-2H-6, 8-methanophenyl [1,3,2] dioxaborane of the formula:
Compound 3 b: 2, 2-difluoro-4- (4-bromophenyl) -7, 7-dimethyl-5, 6,7, 8-tetrahydro-2H-6, 8-methanophenyl [1,3,2] dioxaborane of the formula:
the synthesis method of the nopinyl beta-diketone boron difluoride complex comprises the following process steps:
(1) Taking nopinone as an initial raw material, taking sodium hydride as a catalyst, and carrying out claisen condensation reaction with aromatic esters with different substituents to obtain nopinonyl beta-diketone;
(2) performing complex reaction on nopinyl beta-diketone and boron trifluoride diethyl etherate to obtain a nopinyl beta-diketone boron difluoride complex;
In the step (1), the nopinone and aromatic ester with different substituent groups are subjected to claisen condensation to obtain nopinonyl beta-diketone, and the specific preparation method comprises the following steps:
1) adding 0.06mol of sodium hydride into a reaction container, slowly injecting 8mL of ethylene glycol dimethyl ether under the protection of nitrogen, dissolving 0.02mol of nopinone in 9mL of ethylene glycol dimethyl ether, then slowly injecting into the reaction container under the protection of nitrogen, heating and refluxing for 0.5h while controlling the reaction temperature at 82 ℃, slowly injecting 0.024mol of aromatic ester into the reaction container under the protection of nitrogen after dissolving 9mL of ethylene glycol dimethyl ether, tracking the reaction process by thin layer chromatography, and reacting for 7-8 h;
2) Extracting the reactant with 100mL ethyl acetate for 3 times, combining organic phases, and washing with saturated saline solution for several times until the reactant is neutral; drying the organic phase by anhydrous sodium sulfate, filtering, concentrating and recovering the solvent to obtain nopinyl beta-diketone;
3) recrystallizing with methanol to obtain nopaline beta-diketone.
In the step (2), the nopinyl beta-diketone and boron trifluoride diethyl etherate carry out complex reaction to obtain the nopinyl beta-diketone boron difluoride complex, and the specific preparation method comprises the following steps:
1) adding 0.02mol of nopinone beta-diketone compound, 0.10mol of boron trifluoride ether and 20mL of dichloromethane into a reaction vessel, heating in an oil bath, and carrying out reflux reaction for 5h at the temperature of 45 ℃;
2) Extracting the reaction solution with saturated salt solution for 3 times until the reaction solution is neutral, combining organic phases, drying the organic phases with anhydrous sodium sulfate, filtering, concentrating and recovering the solvent to obtain a crude nopinonyl beta-diketone boron difluoride complex product;
3) Recrystallizing the crude nopinyl beta-diketone boron difluoride complex product by using methanol to obtain a yellow blocky nopinyl beta-diketone boron difluoride complex crystal.
The nopinyl beta-diketone boron difluoride complex is applied as a luminescent material.
The nopinyl beta-diketone boron difluoride complex is applied to an electroluminescent device.
the luminescent material is applied to an electroluminescent device, the device presents blue-green light, and the luminous efficiency is 7.09 lm/W.
the invention takes an oxidation product nopinone of natural renewable resource beta-pinene as a raw material, and the nopinone alkyl beta-diketone is generated by claisen condensation with aromatic ester with different substituents; the nopinyl beta-diketone reacts with boron trifluoride diethyl etherate to obtain the nopinyl beta-diketone boron difluoride complex. The compounds are found to show blue-green fluorescence, and can be used as luminescent materials to be applied to electroluminescent devices.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the nopinone is used as a derivative of renewable resource beta-pinene, has high yield and low price, and is beneficial to industrial production.
(2) the synthesis process of nopinyl beta-diketone has the advantages of simple synthesis operation, high yield and the like, and meets the requirement of sustainable development.
(3) The synthesis of the nopaline beta-diketone boron difluoride complex compound has important significance for expanding deep processing and comprehensive utilization channels of turpentine in China and improving the application value of the turpentine.
(4) The compound shows blue-green fluorescence, can be used as a luminescent material to be applied to an electroluminescent device, and the device shows blue-green light.
Drawings
FIG. 1 is a diagram of the electroluminescence wavelengths of device I and their CIE chromaticity coordinates;
FIG. 2 is a diagram of the electroluminescence wavelength of device II and its CIE chromaticity coordinate.
Detailed description of the preferred embodiments
The invention is further described below with reference to specific embodiments.
Example 1
1) Preparation of nopinyl beta-diketones
adding 0.06mol of sodium hydride into a reaction vessel, slowly injecting 8mL of ethylene glycol dimethyl ether under the protection of nitrogen, dissolving 0.02mol of nopinone in 9mL of ethylene glycol dimethyl ether, then slowly injecting into the reaction vessel under the protection of nitrogen, heating and refluxing for 0.5h while controlling the reaction temperature at 82 ℃, slowly injecting 0.024mol of aromatic ester 1a and 1b into the reaction vessel under the protection of nitrogen after dissolving 9mL of ethylene glycol dimethyl ether, tracking the reaction process by thin layer chromatography, and reacting for 7-8 h. The reactant is extracted by 100mL ethyl acetate for 3 times, and the organic phase is concentrated and the solvent is recovered to obtain the crude product of the nopinone beta-diketone compound. Recrystallizing with methanol to obtain nopinone alkyl beta-diketone 2a and 2b, wherein the structural formulas of 2a and 2b are as follows:
The nopinyl beta-diketones 2a and 2b obtained by the synthesis were characterized, and the results are as follows:
Compound 2 a: yellow solid, yield 65.7%, melting point 112.2-113.2 ℃; 1H NMR (400MHz, CDCl3) δ:15.79(s,1H), 7.77-7.68 (m,2H), 6.97-6.94 (m,2H),3.86(s,3H),2.73(d, J ═ 3.0Hz,2H), 2.60-2.51 (m,2H),2.30(tt, J1 ═ 5.7Hz, J2 ═ 2.9Hz,1H),1.46(d, J ═ 9.2Hz,1H),1.35(s,3H),0.96(s, 3H); 13C NMR (100MHz, CDCl3) delta 208.76,172.94,161.13,130.05,127.72,113.57,103.09,55.35,54.64,39.99,39.47,28.66,27.86,25.82, 21.49; HRMS (M/z) [ M + Na ] + calculated for C17H20O3+ Na +, 295.1297; found, 295.1305.
Compound 2 b: the yield of yellow solid is 59.1 percent, and the melting point is 132.8-133.5 ℃; 1H NMR (400MHz, CDCl3) δ:15.51(s,1H),7.60(s,4H),2.69(t, J ═ 2.9Hz,2H), 2.63-2.53 (m,2H),2.31(tt, J1 ═ 6.0Hz, J2 ═ 3.1Hz,1H),1.47(d, J ═ 9.6Hz,1H),1.37(s,3H),0.98(s, 3H); 13C NMR (100MHz, CDCl3) delta 209.42,171.40,134.07,131.50,129.79,124.66,104.06,54.77,39.80,39.56,28.26,27.73,25.81, 21.55; HRMS (M/z) [ M + Na ] + calculated for C16H17BrO2+ Na +, 343.0297; found, 343.0304.
2) Preparation of nopinyl beta-diketone boron difluoride complex
0.02mol of nopinyl beta-diketone, 0.10mol of boron trifluoride ether and 20mL of dichloromethane are added into a reaction vessel, heated in an oil bath and refluxed for 5 hours at the temperature of 45 ℃. Extracting the reaction solution with saturated saline solution for 3 times until the reaction solution is neutral, and combining organic phases; concentrating the organic phase to recover the solvent and obtain the crude nopinyl beta-diketone boron difluoride complex. Recrystallizing the crude nopinyl beta-diketone boron difluoride complex product by using methanol to obtain yellow powdery nopinyl beta-diketone boron difluoride complexes 3a and 3 b.
Characterization of the resulting nopinyl β -diketone boron difluoride complexes 3a and 3b with the following data:
Complex 3 a: the yield of yellow solid is 89.3 percent, and the melting point is 147.6-148.6 ℃; 1H NMR (400MHz, CDCl3) δ 8.04 to 7.96(m,2H),7.04 to 6.92(m,2H),3.90(s,3H),2.89(dd, J1 ═ 14.6Hz, J2 ═ 3.0Hz,2H),2.77(t, J ═ 5.6Hz,1H),2.73 to 2.60(m,1H),2.42(tt, J1 ═ 5.9Hz, J2 ═ 3.0Hz,1H),1.49(d, J ═ 10.0Hz,1H),1.42(s,3H),0.97(s, 3H); 13CNMR (100MHz, CDCl3) delta 200.80,178.45,163.72,132.26,125.68,114.05,103.54,55.61,51.17,40.31,39.90,28.80,28.57,25.50, 21.39; HRMS (M/z) [ M + Na ] + calculated for C17H19BF2O3+ Na +, 343.1297; found, 343.1288.
complex 3 b: the yield of yellow solid is 86.9 percent, and the melting point is 175.2-176.2 ℃; 1H NMR (400MHz, CDCl3) δ 7.83-7.74 (m,2H),7.69-7.59(m,2H), 2.91-2.75 (m,3H),2.71(dd, J1 ═ 10.6Hz, J2 ═ 5.8Hz,1H),2.43(tt, J1 ═ 5.9Hz, J2 ═ 3.1Hz,1H),1.49(d, J ═ 10.2Hz,1H),1.43(s,3H),0.97(s, 3H); 13C NMR (100MHz, CDCl3) delta 203.26,178.01,132.21,131.97,130.81,128.07,104.57,51.45,40.56,39.71,28.41,28.20,25.50, 21.47; HRMS (M/z) [ M + Na ] + calculated for C16H16BBrF2O2+ Na +, 391.0297; found, 391.0287.
example 2
The nopinyl beta-diketone boron difluoride complex is applied to an electroluminescent device as a luminescent material.
1) weighing the conductive adhesive A and the curing agent B by using an electronic scale of 0.001g, wherein the weight ratio is 1: 4.
2) the conductive adhesive A needs to be stirred for more than 2min before being used for adhesion. And mixing the conductive adhesive A and the fluorescent powder, fully stirring, and adding the curing agent B. The stirring time is generally 5min after the curing agent B glue is added. The phosphor powder and the glue are mixed evenly and defoamed for standby.
3) The fluorescent glue without bubbles is stirred properly before dispensing. The optimal point is that the support is full of cups and protrudes a little, but the support cannot overflow, and the glue is baked to be dry and is flat.
4) Baking conditions: 60 ℃/40min +135 ℃/90 min. And (3) baking in an oven within the first time after dispensing, wherein the baking at the temperature of 60 ℃/40min is mainly used for fully mixing the glue A, the fluorescent powder and the glue B curing agent to prepare for curing.
TABLE 1 electroluminescent properties of devices I and II
| Device | VF(V) | IF(mA) | EL(nm) | ηP(lm/W) | TC(K) | CIE(x,y) | Ra |
| Device I | 3.08 | 9.9 | 499.2 | 7.08 | 7028 | (0.2774,0.4531) | 54.4 |
| component II | 3.06 | 9.9 | 500.4 | 2.79 | 6087 | (0.3084,0.4800) | 55.4 |
Table 1 shows the electroluminescent properties of devices I and II made with nopinyl beta-diketone boron difluoride complexes 3a and 3b as the luminescent materials. The electroluminescence wavelengths of the device I and the device ii are shown in fig. 1 and fig. 2, and it can be obtained from table 1 that the device I made of 3a as a luminescent material has better electroluminescence property, and under the conditions of voltage 3.08V and voltage 9.9mA, the device I emits blue-green light, and the CIE chromaticity coordinate, emission wavelength, color temperature, color rendering index, and luminous efficiency are respectively: (0.2774,0.4531), 499.2nm, 7028K, 54.4 and 7.08 lm/W. The nopaline beta-diketone boron difluoride complex has good application value in electroluminescent devices.
Claims (7)
1. The nopinyl beta-diketone boron difluoride complex is characterized in that the structural formula is as follows:
in the formula: r is OCH3 and Br.
2. The method of preparing a nopinyl β -diketone boron difluoride complex of claim 1 comprising the steps of:
(1) Taking nopinone as an initial raw material, taking sodium hydride as a catalyst, and carrying out claisen condensation reaction with aromatic esters with different substituents to obtain a crude nopinonyl beta-diketone extract;
(2) The nopinyl beta-diketone reacts with boron trifluoride diethyl etherate to obtain the nopinyl beta-diketone boron difluoride complex.
3. the method of preparing a nopinyl β -diketone boron difluoride complex according to claim 2, characterized in that: in the step (1), the specific synthesis steps of nopinyl beta-diketone are as follows:
1) adding 0.06mol of sodium hydride into a reaction container, slowly injecting 8mL of ethylene glycol dimethyl ether under the protection of nitrogen, dissolving 0.02mol of nopinone in 9mL of ethylene glycol dimethyl ether, then slowly injecting into the reaction container under the protection of nitrogen, heating and refluxing for 0.5h while controlling the reaction temperature at 82 ℃, slowly injecting 0.024mol of aromatic ester into the reaction container under the protection of nitrogen after dissolving 9mL of ethylene glycol dimethyl ether, tracking the reaction process by thin layer chromatography, and reacting for 7-8 h;
2) Extracting the reactant with 100mL ethyl acetate for 3 times, combining organic phases, and washing with saturated saline solution for several times until the reactant is neutral; drying the organic phase by anhydrous sodium sulfate, filtering, concentrating and recovering the solvent to obtain a crude nopinonyl beta-diketone product;
3) recrystallizing with methanol to obtain nopinyl beta-diketone.
4. The method of preparing a nopinyl β -diketone boron difluoride complex according to claim 2, characterized in that: in the step (2), the specific synthesis steps of the nopinyl beta-diketone boron difluoride complex are as follows:
1) Adding 0.02mol of nopinyl beta-diketone, 0.10mol of boron trifluoride ether and 20mL of dichloromethane into a reaction vessel, heating in an oil bath, and carrying out reflux reaction at 45 ℃ for 3 h;
2) Extracting the reaction solution with saturated salt solution for 3 times until the reaction solution is neutral, combining organic phases, drying the organic phases with anhydrous sodium sulfate, filtering, concentrating and recovering the solvent to obtain a crude nopinonyl beta-diketone boron difluoride complex product;
3) recrystallizing the crude nopinyl beta-diketone boron difluoride complex product by using methanol to obtain a yellow blocky nopinyl beta-diketone boron difluoride complex crystal.
5. use of the nopinyl β -diketone boron difluoride complex of claim 1 as a luminescent material.
6. The use of the nopinyl β -diketone boron difluoride complex of claim 1 in an electroluminescent device.
7. Use according to claim 6 as a light-emitting material in an electroluminescent device, the device exhibiting bluish-green light.
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Granted publication date: 20191206 |