CN102942444A - 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 of 2,2'-two bromo-9, the synthetic method of 9'-spiral shell two fluorenes.
Background technology
Since the last century the eighties, the research of electroluminescent organic material (OLED) develops rapidly.The advantages such as active illuminating, brightness height, high-contrast, fast response time, driving voltage are low because OLED has, good stability, good film-forming property have a wide range of applications in fields such as illumination, instrument, instrument demonstrations.Spirobifluorene derivative has important using value in the organic electroluminescent field, and it has many advantages, as reducing 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 the extension of three-dimensional, can be to 2,2 '-position and 2,2 ', 7,7 '-position is modified, is designed and synthesize the luminescent material with unique function.To 2,2 of spiral shell two fluorenes '-to carry out structural modification be that 9'-spiral shell two fluorenes are initiator with 2,2'-, two bromo-9 mostly in the position, it is a kind of very important OLED material intermediate.About 2,2'-, two bromo-9, the synthetic method of 9'-spiral shell two fluorenes mainly contains following two kinds at present:
Method one is raw material with 9,9'-spiral shell, two fluorenes, through one the 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, and following shortcoming is arranged:
(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-, two bromos, and wherein 2,7-two bromo impurity are difficult to separate with target compound, bring very large difficulty for the purifying of product.
Method two, take trimethyl silicon based phenylo boric acid as raw material, through a step linked reaction, again through nucleophilic substitution, bromo-reaction and ring closure reaction, finally obtain target compound 2 first, 2'-two 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 provides a kind of cost, and purification process is simple 2,2'-two 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'-two bromo-9, the synthetic method of 9'-spiral shell two fluorenes, its synthesis technique is: take the 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, namely get described 2,2'-two 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, and 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, obtain 2,2'-, two bromo-9 through nucleophilic substitution, bromo-reaction, ring closure reaction, 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 are 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 the reaction solvent one, stir, then drip n-Butyl Lithium, after the 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 the methyl tertiary butyl ether etc.
Further, the 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 the reaction solvent two, after stirring, add brominated reagent again and 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, the iron powder;
Described reaction solvent two comprises any one or a few the mixing in ethylene dichloride, chloroform or the tetracol phenixin;
Described brominated reagent comprises that bromine, NBS or hydrogen bromide add any one in the 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, can adopt illumination to cause when selecting NBS, also can add BPO (benzoyl peroxide), AIBN (Diisopropyl azodicarboxylate) makees initiator, the mol ratio of initiator and Compound I is 0.1～0.5:1.0.
Further, the processing condition that described adding brominated reagent reacts are: be under 30 ℃～100 ℃ the condition in temperature of reaction, and 2～24 hours reaction times.
Further, the concrete steps of described ring closure reaction are: Compound I I is joined in the reaction solvent three, and stirring reaction is complete, namely obtain described 2,2'-two 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'-, two bromo-9 after 9'-spiral shell two fluorenes are synthetic, all add recrystallization solvent and carry out recrystallization.
Described recrystallization solvent comprises the (mixing of any one or a few in C1～C4), Isosorbide-5-Nitrae-dioxane, DMF, the tetrahydrofuran (THF) of hexanaphthene, normal hexane, sherwood oil, methylene dichloride, ethylene dichloride, chloroform, ethyl acetate, acetone, toluene, dimethylbenzene, low-carbon alcohol.
Description of drawings
Fig. 1 is among the present invention 2,2'-two bromo-9,9'-spiral shell two fluorenes
1HNMR figure;
Fig. 2 is among the present invention 2,2'-two bromo-9,9'-spiral shell two fluorenes
1HNMR figure;
Fig. 3 is among the present invention 2,2'-two bromo-9,9'-spiral shell two fluorenes
1HNMR figure;
Fig. 4 is among the present invention 2,2'-two 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, institute gives an actual example and only is used for explaining the present invention, is not be used to limiting scope of the present invention.
Synthesizing of embodiment 1 Compound I
Take into account sleeve pipe, fluid-tight, mechanical stirring, constant pressure funnel and drying tube in 2L there-necked flask installation N2 side pipe, temperature.In the 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.In-78 ℃ of lower 477mL (1.05mol) n-Butyl Lithiums (2.2M hexane solution) that drip, dropwised 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 gets white solid.Add the toluene recrystallization in above-mentioned white solid, the room temperature suction filtration gets the white powder solid, yield 85.6%, HPLC purity 99.5%.
MS:(EI):m/z=334([M+])。
At the 2L there-necked flask temperature is installed and takes into account sleeve pipe, fluid-tight, mechanical stirring, constant pressure funnel and drying tube.Add 120g Compound I, 1000g ethylene dichloride and aluminum trichloride (anhydrous) in the 2L there-necked flask, mechanical stirring drips 172g (1.08mol) bromine in system, dropwises and is warming up to 80 ℃ of interior temperature, insulation reaction 6h.
Be incubated complete after, room temperature is down in water-bath, drips saturated sodium bisulfite solution in system, mechanical stirring 0.5 hour, suction filtration, water wash twice obtains faint yellow solid.Add acetone recrystallization 3 times, the 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 32,2'-two bromo-9,9'-spiral shell two fluorenes synthetic
At the 2L there-necked flask temperature is installed and takes into account sleeve pipe, mechanical stirring, spherical condensation tube.Add 100g (0.20mol) Compound I I, 1200g methylsulfonic acid in the 2L there-necked flask, mechanical stirring is warming up to and bathes 130 ℃ of temperature, insulation reaction 8 hours.
Be incubated complete after, suction filtration, washing filter cake 2-3 time obtains the grey black solid.Add the methylene dichloride recrystallization, be down to the room temperature suction filtration, obtain the white powder solid, yield 81.3%, HPLC purity 99.3%.(nuclear magnetic spectrum is seen 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(CDC?l?3，125MHz)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
Take into account sleeve pipe, fluid-tight, mechanical stirring, constant pressure funnel and drying tube in 2L there-necked flask installation N2 side pipe, temperature.In the 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.In-78 ℃ of lower 477mL (1.05mol) n-Butyl Lithiums (2.2M hexane solution) that drip, dropwised 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 gets white solid.In above-mentioned white solid, add the toluene recrystallization, get the white powder solid, yield 82.7%, HPLC purity 99.4%.
Embodiment 5 Compound I I's is synthetic
At the 2L there-necked flask temperature is installed and takes into account sleeve pipe, fluid-tight, mechanical stirring, constant pressure funnel and drying tube.Add 120g Compound I, 1000g ethylene dichloride and aluminum trichloride (anhydrous) in the 2L there-necked flask, mechanical stirring drips 230.4g (1.44mol) bromine in system, dropwises and is warming up to 80 ℃ of interior temperature, insulation reaction 6h.
Be incubated complete after, room temperature is down in water-bath, drips saturated sodium bisulfite solution in system, mechanical stirring 0.5 hour, suction filtration, water wash twice obtains faint yellow solid.Add acetone recrystallization three times, obtain white solid, yield 78.8%, HPLC purity 99%.
Embodiment 62,2'-two bromo-9,9'-spiral shell two fluorenes synthetic
At the 2L there-necked flask temperature is installed and takes into account sleeve pipe, mechanical stirring, spherical condensation tube.Add 100g (0.20mo l) Compound I I, 1300g trifluoromethanesulfonic acid in the 2L there-necked flask, mechanical stirring is warming up to and bathes 130 ℃ of temperature, insulation reaction 8 hours.
Be incubated complete after, suction filtration, washing filter cake 2～3 times obtains the grey black solid.Add the methylene dichloride recrystallization, be down to the room temperature suction filtration, obtain the white powder solid, yield 82.1%, HPLC purity 99.4%.
The above only is preferred embodiment of the present invention, and is in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. one kind 2,2'-two bromo-9, the synthetic method of 9'-spiral shell two fluorenes is characterized in that, its synthesis technique is: take the 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, namely gets described 2,2'-two 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.
2. according to claim 12,2'-two 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 the reaction solvent one, stir, then drip n-Butyl Lithium, insulation reaction drips methylcarbonate or diethyl carbonate after 0.5～3 hour again, 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'-two bromo-9, 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 the methyl tertiary butyl ether.
4. according to claim 22,2'-two bromo-9, the synthetic method of 9'-spiral shell two fluorenes is characterized in that, the 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'-two 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 the reaction solvent two, after stirring, add again brominated reagent and 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'-two bromo-9, the synthetic method of 9'-spiral shell two fluorenes is characterized in that, described catalyzer is any one in iron trichloride, aluminum chloride, the iron powder; Described reaction solvent two is any one or a few the mixing in ethylene dichloride, chloroform or the tetracol phenixin; Described brominated reagent is that bromine, NBS or hydrogen bromide add any one in the hydrogen peroxide.
7. according to claim 52,2'-two bromo-9, the synthetic method of 9'-spiral shell two fluorenes is characterized in that, the processing condition that described adding brominated reagent reacts are: be under 30 ℃～100 ℃ the condition in temperature of reaction, 2～24 hours reaction times.
8. according to claim 12,2'-two 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 the reaction solvent three, and stirring reaction is complete, namely obtain described 2,2'-two 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'-two bromo-9, 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'-two bromo-9, the synthetic method of 9'-spiral shell two fluorenes is characterized in that, and the temperature of reaction of described ring closure reaction is 100 ℃～160 ℃, and the reaction times is 6～10 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN116396497A (en) * | 2023-06-05 | 2023-07-07 | 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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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN116396497A (en) * | 2023-06-05 | 2023-07-07 | 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 |
| 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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