CN102942444B - Synthesis method of 2,2'-dibromo-9,9'-spirobifluorene - Google Patents
Synthesis method of 2,2'-dibromo-9,9'-spirobifluorene Download PDFInfo
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Abstract
The invention relates to a synthesis method of 2,2'-dibromo-9,9'-spirobifluorene. A synthesis process comprises the steps that 2-brominated biphenyl is used as raw materials, the 2-brominated biphenyl and methyl carbonate or diethyl carbonate generate intermediate compounds I through nucleophilic substitution reaction, the compounds I generate compounds II through bromination reaction, finally, the ring closing reaction is carried out, and the 2,2'-dibromo-9,9'-spirobifluorene is obtained. The synthesis method has the advantages that the synthesis path selection is reasonable, the selected raw materials are economic, the obtaining is easy, the 2,2'-dibromo-9,9'-spirobifluorene is obtained through nucleophilic substitution, bromination reaction and ring closing reaction, the total yield can reach 50 percent, and the HPLC (high performance liquid chromatography) purity of final products is greater than 99 percent. The reaction is easy to control, and in addition, the purification method of all intermediates and final products is simple.
Description
Technical field
The present invention relates to a kind ofly 2,2'-bis-is bromo-9, the synthetic method of 9'-spiral shell two fluorenes.
Background technology
Since last century the eighties, the research of electroluminescent organic material (OLED) develops rapidly.Because OLED has that active illuminating, brightness are high, the advantage such as low, the good stability of high-contrast, fast response time, driving voltage, good film-forming property, in fields such as illumination, instrument, instrument demonstrations, have a wide range of applications.Spirobifluorene derivative has important using value in organic electroluminescent field, and it has many advantages, as reduced molecular interaction and then improving luminous efficiency, improve solvability etc.2,2 of spiral shell two fluorenes '-position and 2,2 ', 7,7 '-position has good reactive behavior, for its structure is provided convenience to three-dimensional extension, can be to 2,2 '-position and 2,2 ', 7,7 '-position is modified, and designs and synthesizes the luminescent material with unique function.To 2,2 of spiral shell two fluorenes ' and to carry out structural modification be bromo-9 with 2,2'-bis-mostly in-position, and 9'-spiral shell two fluorenes are initiator, and it is a kind of very important OLED material intermediate.Bromo-9 about 2,2'-bis-at present, the synthetic method of 9'-spiral shell two fluorenes mainly contains following two kinds:
Method one, with 9,9'-spiral shell, two fluorenes for raw material, through a step bromo-reaction obtain target compound (J.Org.Chem.2002,67,4924-4936), reaction equation is as follows:
Although this synthetic route is short, only has single step reaction, there is following shortcoming:
(a) 9,9'-spiral shell two fluorenes costs are higher, and reaction yield is not high, and economy is bad.
(b) reaction process adopts the direct bromo-reaction of bromine, can produce the impurity of single bromo, three bromos, many bromos and 2,7-, bis-bromos, and wherein 2, it is separated that 7-bis-bromo impurity and target compound are difficult to, and brings very large difficulty to the purifying of product.
Method two, take trimethyl silicon based phenylo boric acid as raw material, first through a step linked reaction, then through nucleophilic substitution, bromo-reaction and ring closure reaction, finally obtain target compound 2,2'-bis-bromo-9,9'-spiral shell two fluorenes (Organic Letters, 2005,17,3717-3720), concrete synthetic route is as follows:
Reaction equation:
The shortcoming of this synthetic route is as follows:
(a) the trimethyl silicon based phenylo boric acid of raw material is expensive.
(b) synthetic route is longer, and yield is lower, finally causes synthetic cost very high.
Summary of the invention
It is lower that technical problem to be solved by this invention is to provide a kind of cost, and purification process is simple 2, and 2'-bis-is bromo-9, the synthetic method of 9'-spiral shell two fluorenes.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of 2,2'-bis-bromo-9, the synthetic method of 9'-spiral shell two fluorenes, its synthesis technique is: take 2-bromo biphenyl as raw material, by nucleophilic substitution reaction and methylcarbonate or diethyl carbonate generation midbody compound I, Compound I generates Compound I I through bromo-reaction again, finally by ring closure reaction, obtain describedly 2,2'-bis-is bromo-9,9'-spiral shell two fluorenes;
Wherein, the synthetic route of described synthetic method is as follows:
The mol ratio of described 2-bromo biphenyl and described methylcarbonate or diethyl carbonate is 2.0～4.0:1.0.
The invention has the beneficial effects as follows: cost of the present invention is low, preparation and purification process are simple, and the by product of generation is few.Synthetic route of the present invention is selected rationally, selected raw material all economical, be easy to get, through nucleophilic substitution, bromo-reaction, ring closure reaction, obtain 2,2'-bis-bromo-9,9'-spiral shell two fluorenes, total recovery can reach 50%, the HPLC purity of final product is greater than 99%.The present invention reacts easy control, and all intermediates and final product purification process simple.
On the basis of technique scheme, the present invention can also do following improvement.
Further, the concrete steps of described nucleophilic substitution reaction are: described 2-bromo biphenyl is joined in reaction solvent one, stir, then drip n-Butyl Lithium, after insulation reaction 0.5～3 hour, drip methylcarbonate or diethyl carbonate, insulation reaction 0.5～3 hour, obtains midbody compound I again; Wherein, the mol ratio of described n-Butyl Lithium and described methylcarbonate or diethyl carbonate is 2.0～4.0:1.0.
Further, described reaction solvent one comprises any one in tetrahydrofuran (THF), anhydrous diethyl ether or methyl tertiary butyl ether etc.
Further, temperature of reaction during described dropping n-Butyl Lithium is-60 ℃～-78 ℃; Temperature of reaction when described dropping methylcarbonate or diethyl carbonate is-30 ℃～-60 ℃.
Further, the concrete steps of described bromo-reaction are: midbody compound I and catalyzer are joined in reaction solvent two, after stirring, then add brominated reagent to react, obtain Compound I I;
Wherein, described catalyst quality is 0.5%～5% of Compound I quality; The mol ratio of described brominated reagent and Compound I is 2.0～8.0:1.0.
Further, described catalyzer comprises any one in iron trichloride, aluminum chloride, iron powder;
Described reaction solvent two comprises any one or a few the mixing in ethylene dichloride, chloroform or tetracol phenixin;
Described brominated reagent comprises that bromine, NBS or hydrogen bromide add any one in hydrogen peroxide.When brominated reagent selects hydrogen bromide to add hydrogen peroxide, the mol ratio of hydrogen bromide and hydrogen peroxide is 1.0～3.0:1.0, while selecting NBS, can adopt illumination to cause, also can add BPO (benzoyl peroxide), AIBN (Diisopropyl azodicarboxylate) to make initiator, the mol ratio of initiator and Compound I is 0.1～0.5:1.0.
Further, described in add the processing condition that brominated reagent reacts to be: in temperature of reaction, be under the condition of 30 ℃～100 ℃, 2～24 hours reaction times.
Further, the concrete steps of described ring closure reaction are: Compound I I is joined in reaction solvent three, and stirring reaction is complete, obtain describedly 2, and 2'-bis-is bromo-9,9'-spiral shell two fluorenes;
Wherein, described reaction solvent three is 10～30:1 with the mass ratio of Compound I I.
Further, described reaction solvent three is methylsulfonic acid and/or trifluoromethanesulfonic acid.Both make solvent and also made dewatering agent.
Further, the temperature of reaction of described ring closure reaction is 100 ℃～160 ℃, and the reaction times is 6～10 hours.
Further, described midbody compound I, Compound I I and 2,2'-bis-are bromo-9, after 9'-spiral shell two fluorenes are synthetic, all add recrystallization solvent to carry out recrystallization.
Described recrystallization solvent comprises any one or a few the mixing in hexanaphthene, normal hexane, sherwood oil, methylene dichloride, ethylene dichloride, chloroform, ethyl acetate, acetone, toluene, dimethylbenzene, low-carbon alcohol (C1～C4), Isosorbide-5-Nitrae-dioxane, DMF, tetrahydrofuran (THF).
Accompanying drawing explanation
Fig. 1 is in the present invention 2, and 2'-bis-is bromo-9,9'-spiral shell two fluorenes
1hNMR figure;
Fig. 2 is in the present invention 2, and 2'-bis-is bromo-9,9'-spiral shell two fluorenes
1hNMR figure;
Fig. 3 is in the present invention 2, and 2'-bis-is bromo-9,9'-spiral shell two fluorenes
1hNMR figure;
Fig. 4 is in the present invention 2, and 2'-bis-is bromo-9,9'-spiral shell two fluorenes
13cNMR figure.
Embodiment
Below in conjunction with accompanying drawing, principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Synthesizing of embodiment 1 Compound I
In 2L there-necked flask installation N2 side pipe, temperature, take into account sleeve pipe, fluid-tight, mechanical stirring, constant pressure funnel and drying tube.In 2L there-necked flask, add 244.7g (1.05mol) 2-bromo biphenyl and 600g tetrahydrofuran (THF), mechanical stirring, nitrogen protection, low temperature is bathed cooling.At-78 ℃, drip 477mL (1.05mol) n-Butyl Lithium (2.2M hexane solution), dropwise insulation reaction 1.5 hours.Insulation finishes to drip 45g (0.5mol) methylcarbonate to system, dropwises-78 ℃ and continues insulation 2 hours, is transferred to stirring at room 3～4 hours.
Reaction finishes to add 200mL water in system, mechanical stirring 30 minutes, and suction filtration obtains white solid.In above-mentioned white solid, add toluene recrystallization, room temperature suction filtration, obtains white powder solid, yield 85.6%, HPLC purity 99.5%.
MS:(EI):m/z=334([M+])。
Embodiment 2 Compound I I's is synthetic
At 2L there-necked flask, temperature is installed and takes into account sleeve pipe, fluid-tight, mechanical stirring, constant pressure funnel and drying tube.In 2L there-necked flask, add 120g Compound I, 1000g ethylene dichloride and aluminum trichloride (anhydrous), mechanical stirring, drips 172g (1.08mol) bromine in system, dropwises and is warming up to 80 ℃ of interior temperature, insulation reaction 6h.
After insulation, room temperature is down in water-bath, in system, drips saturated sodium bisulfite solution, mechanical stirring 0.5 hour, and suction filtration, water wash twice, obtains faint yellow solid.Add acetone recrystallization 3 times, room temperature suction filtration, obtains white solid, yield 74.2%, HPLC purity 99%
1HNMR(CDCl3，500MHz)δ：7.41～7.43(2H,d)，7.38～7.41(2H,t)，7.31～7.33(4H,d)，7.25～7.28(2H,t)，7.13～7.15(2H,d)，6.95～6.97(4H,d)
13CNMR(CDCl3，125MHz)δ：199.5,140.5,139.3,138.9，131.06,131.04,130.74,130.5,130.3,127.1,121.6。
Embodiment 32, and 2'-bis-is bromo-9,9'-spiral shell two fluorenes synthetic
At 2L there-necked flask, temperature is installed and takes into account sleeve pipe, mechanical stirring, spherical condensation tube.In 2L there-necked flask, add 100g (0.20mol) Compound I I, 1200g methylsulfonic acid, mechanical stirring, is warming up to and bathes 130 ℃ of temperature, insulation reaction 8 hours.
After insulation, suction filtration, washing filter cake 2-3 time, obtains grey black solid.Add methylene dichloride recrystallization, be down to room temperature suction filtration, obtain white powder solid, yield 81.3%, HPLC purity 99.3%.(nuclear magnetic spectrum is shown in accompanying drawing 1～4)
1HNMR(CDCl3，500MHz)δ：6.70～6.72(2H，d)，6.83～6.84(2H，d)，7.12～7.15(2H，t)，7.36～7.39(2H，t)，7.49～7.51(2H，dd)，7.69～7.71(2H，d)，7.80～7.82(2H，d)
13CNMR(CDCl3，125MHz)δ：149.9,147.7,140.7,140.6,131.2,128.4,128.2,127.3,124.1,121.5,121.4,120.2,65.6。
Synthesizing of embodiment 4 Compound I
In 2L there-necked flask installation N2 side pipe, temperature, take into account sleeve pipe, fluid-tight, mechanical stirring, constant pressure funnel and drying tube.In 2L there-necked flask, add 244.7g (1.05mol) 2-bromo biphenyl and 600g tetrahydrofuran (THF), mechanical stirring, nitrogen protection, low temperature is bathed cooling.At-78 ℃, drip 477mL (1.05mol) n-Butyl Lithium (2.2M hexane solution), dropwise insulation reaction 1.5 hours.Insulation finishes to drip 45g (0.5mol) methylcarbonate to system, dropwises-50 ℃ and continues insulation 2 hours, is transferred to stirring at room 3～4 hours.
Reaction finishes to add 200mL water in system, mechanical stirring 30 minutes, and suction filtration obtains white solid.In above-mentioned white solid, add toluene recrystallization, obtain white powder solid, yield 82.7%, HPLC purity 99.4%.
Embodiment 5 Compound I I's is synthetic
At 2L there-necked flask, temperature is installed and takes into account sleeve pipe, fluid-tight, mechanical stirring, constant pressure funnel and drying tube.In 2L there-necked flask, add 120g Compound I, 1000g ethylene dichloride and aluminum trichloride (anhydrous), mechanical stirring, drips 230.4g (1.44mol) bromine in system, dropwises and is warming up to 80 ℃ of interior temperature, insulation reaction 6h.
After insulation, room temperature is down in water-bath, in system, drips saturated sodium bisulfite solution, mechanical stirring 0.5 hour, and suction filtration, water wash twice, obtains faint yellow solid.Add acetone recrystallization three times, obtain white solid, yield 78.8%, HPLC purity 99%.
Embodiment 62, and 2'-bis-is bromo-9,9'-spiral shell two fluorenes synthetic
At 2L there-necked flask, temperature is installed and takes into account sleeve pipe, mechanical stirring, spherical condensation tube.In 2L there-necked flask, add 100g (0.20mol) Compound I I, 1300g trifluoromethanesulfonic acid, mechanical stirring, is warming up to and bathes 130 ℃ of temperature, insulation reaction 8 hours.
After insulation, suction filtration, washing filter cake 2～3 times, obtains grey black solid.Add methylene dichloride recrystallization, be down to room temperature suction filtration, obtain white powder solid, yield 82.1%, HPLC purity 99.4%.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. one kind 2,2'-bis-bromo-9, the synthetic method of 9'-spiral shell two fluorenes, is characterized in that, its synthesis technique is: take 2-bromo biphenyl as raw material, by nucleophilic substitution reaction and methylcarbonate or diethyl carbonate generation midbody compound I, Compound I generates Compound I I through bromo-reaction again, finally by ring closure reaction, obtains described 2,2'-bis-is bromo-9,9'-spiral shell two fluorenes;
Wherein, the synthetic route of described synthetic method is as follows:
The mol ratio of described 2-bromo biphenyl and described methylcarbonate or diethyl carbonate is 2.0～4.0:1.0;
Described brominated reagent is that bromine, NBS or hydrogen bromide add any one in hydrogen peroxide.
2. according to claim 12,2'-bis-bromo-9, the synthetic method of 9'-spiral shell two fluorenes, is characterized in that, the concrete steps of described nucleophilic substitution reaction are: described 2-bromo biphenyl is joined in reaction solvent one, stir, then drip n-Butyl Lithium, insulation reaction is after 0.5～3 hour, then drips methylcarbonate or diethyl carbonate, insulation reaction 0.5～3 hour, obtains midbody compound I; Wherein, the mol ratio of described n-Butyl Lithium and described methylcarbonate or diethyl carbonate is 2.0～4.0:1.0.
3. according to claim 22,2'-bis-is bromo-9, and the synthetic method of 9'-spiral shell two fluorenes, is characterized in that, described reaction solvent one is any one in tetrahydrofuran (THF), anhydrous diethyl ether or methyl tertiary butyl ether.
4. according to claim 22,2'-bis-is bromo-9, and the synthetic method of 9'-spiral shell two fluorenes, is characterized in that, temperature of reaction during described dropping n-Butyl Lithium is-60 ℃～-78 ℃; Temperature of reaction when described dropping methylcarbonate or diethyl carbonate is-30 ℃～-60 ℃.
5. according to claim 12,2'-bis-bromo-9, the synthetic method of 9'-spiral shell two fluorenes, it is characterized in that, the concrete steps of described bromo-reaction are: midbody compound I and catalyzer are joined in reaction solvent two, after stirring, then add brominated reagent to react, obtain Compound I I;
Wherein, described catalyst quality is 0.5%～5% of Compound I quality; The mol ratio of described brominated reagent and Compound I is 2.0～8.0:1.0.
6. according to claim 52,2'-bis-is bromo-9, and the synthetic method of 9'-spiral shell two fluorenes, is characterized in that, described catalyzer is any one in iron trichloride, aluminum chloride, iron powder; Described reaction solvent two is any one or a few the mixing in ethylene dichloride, chloroform or tetracol phenixin.
7. according to claim 52,2'-bis-is bromo-9, and the synthetic method of 9'-spiral shell two fluorenes, is characterized in that, described in add the processing condition that brominated reagent reacts to be: in temperature of reaction, be under the condition of 30 ℃～100 ℃, 2～24 hours reaction times.
8. according to claim 12,2'-bis-is bromo-9, the synthetic method of 9'-spiral shell two fluorenes, it is characterized in that, the concrete steps of described ring closure reaction are: Compound I I is joined in reaction solvent three, and stirring reaction is complete, obtain describedly 2,2'-bis-is bromo-9,9'-spiral shell two fluorenes; Wherein, described reaction solvent three is 10～30:1 with the mass ratio of Compound I I.
9. according to claim 82,2'-bis-is bromo-9, and the synthetic method of 9'-spiral shell two fluorenes, is characterized in that, described reaction solvent three is methylsulfonic acid and/or trifluoromethanesulfonic acid.
10. according to claim 82,2'-bis-is bromo-9, and the synthetic method of 9'-spiral shell two fluorenes, is characterized in that, the temperature of reaction of described ring closure reaction is 100 ℃～160 ℃, and the reaction times is 6～10 hours.
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| CN110845297A (en) * | 2019-11-25 | 2020-02-28 | 山东省海洋化工科学研究院 | Preparation method of 4,4 '-dibromo-9, 9' -spirobifluorene |
| CN112409136A (en) * | 2020-12-12 | 2021-02-26 | 中唯炼焦技术国家工程研究中心有限责任公司 | Method for preparing 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diphenol by efficient clean bromination |
| CN114804994A (en) * | 2021-11-01 | 2022-07-29 | 陕西维世诺新材料有限公司 | Method for preparing substituted aryl fluorene and derivatives thereof |
| CN116396497B (en) * | 2023-06-05 | 2023-10-20 | 吉林省卓材新研科技有限公司 | Metal organic framework material, ligand structure thereof and application of metal organic framework material in nano enzyme |
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| CN1112951A (en) * | 1994-04-07 | 1995-12-06 | 赫彻斯特股份公司 | Spiro-compound and application as electric luminescent material |
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| CN1112951A (en) * | 1994-04-07 | 1995-12-06 | 赫彻斯特股份公司 | Spiro-compound and application as electric luminescent material |
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