CN1986554B - Preparing process of tri (4-ethoxy phenyl) bismuth - Google Patents
Preparing process of tri (4-ethoxy phenyl) bismuth Download PDFInfo
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- CN1986554B CN1986554B CN2005101116985A CN200510111698A CN1986554B CN 1986554 B CN1986554 B CN 1986554B CN 2005101116985 A CN2005101116985 A CN 2005101116985A CN 200510111698 A CN200510111698 A CN 200510111698A CN 1986554 B CN1986554 B CN 1986554B
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Abstract
The present invention discloses preparation process of tri (4-ethoxy phenyl) bismuth. The present invention prepares tri (4-ethoxy phenyl) bismuth with 4-halogeno phenetole as main material, and through reaction with Grignard reagent, which is produced through reaction of alkyl halide, magnesium powder and tetrahydrofuran, and the tetrahydrofuran solution of bismuth trichloride in tetrahydrofuran as reaction solvent. The process of the present invention can obtain tri (4-ethoxy phenyl) bismuth with purity over 99 % and smelting point of 72.4-74.1 deg.c in yield of 80-85 %. Compared with available technology, the present invention has the advantages of mild reaction condition, short reaction period, high product quality, etc and is suitable for industrial production.
Description
Technical field
The present invention relates to the preparation method's of a kind of three (4-ethoxyl phenenyl) bismuth improvement.
Background technology
Three (4-ethoxyl phenenyl) bismuth is a kind of curing catalysts of important macromolecular material, has a wide range of applications in polyurethane material especially.Its structural formula is as follows:
Beilstan 16 898-899 have reported that the diethyl ether solution of using Bromoethyl phenyl ether and bismuth-sodium alloy reacts in the prior art, extracted with diethyl ether, and the method for ethyl alcohol recrystallization preparation three (4-ethoxyl phenenyl) bismuth, yield is 51%.It is reaction raw materials that this preparation method adopts bismuth-sodium alloy, and its preparation needs to react with bismuth metal and sodium, solvent ether, and toxicity is big, easily sets off an explosion, and safe operation process is poor, long reaction time, yield is low, does not have the value of suitability for industrialized production.
Summary of the invention
The technical problem that the present invention solves provides the preparation method of a kind of three (4-ethoxyl phenenyl) bismuth, overcoming poor stability in the prior art, and long reaction time, yield is low, the shortcoming that cost is high.
Technical conceive of the present invention is such: with 4-halogeno-benzene ether is raw material, in tetrahydrofuran (THF) (THF) reaction solvent, react the Grignard reagent that generates with haloalkane, magnesium powder, tetrahydrofuran (THF) respectively, the tetrahydrofuran solution of Trichlorobismuthine reacts, and obtains target product three (4-ethoxyl phenenyl) bismuth.
Method of the present invention comprises the steps:
(1) preparation of Grignard reagent: halogenated alkane, magnesium powder and tetrahydrofuran (THF) reaction solvent under nitrogen atmosphere, are added the elemental halogen initiation reaction, obtain Grignard reagent;
(2) 4-halogeno-benzene ether is added in the tetrahydrofuran (THF) reaction solvent, add in the Grignard reagent of step (1) in 1-2 hour, backflow 2-5 hour, reaction solution was cooled to room temperature;
(3) Trichlorobismuthine is added in the tetrahydrofuran (THF) reaction solvent, add in the reaction solution of step (2) in 0.5-1.5 hour, backflow 1-3 hour, from reaction product, collect three (4-ethoxyl phenenyl) bismuth crude product then, use the mixed solvent recrystallization, obtain target product.
According to the present invention, said 4-halogeno-benzene ether is a 4-chlorinated benzene ether, 4-bromobenzene ether, a kind of in the 4-phenyl-iodide ether.
Said halogenated alkane is any in chloric ethane, bromic ether, chloro-propane or the bromo propane; Elemental halogen is a kind of in simple substance bromine or the iodine.
The ratio of components of reactant is a 4-halogeno-benzene ether: magnesium powder: Trichlorobismuthine=1: 1-1.20: 0.28-0.34, mol ratio.
The ratio of components of reaction solvent is a 4-halogeno-benzene ether: tetrahydrofuran (THF)=1: 100-350, molecular volume ratio; Trichlorobismuthine: tetrahydrofuran (THF)=1: 2.5-3.5, mass volume ratio.
The present invention collects three (4-ethoxyl phenenyl) bismuth crude product and comprises the steps: under the room temperature from reaction product, reaction product adds in the inorganic acid solution, and with benzene extraction, washing, drying is filtered, and steaming desolventizes, and obtains crude product;
Said inorganic acid solution is a kind of in hydrochloric acid soln or the sulphuric acid soln, and its concentration is 15-30wt%;
The mixed solvent of forming with benzene and ethanol carries out recrystallization to three (4-ethoxyl phenenyl) bismuth crude product, and the consumption of mixed solvent is a 4-halogeno-benzene ether: mixed solvent=1.0: 5.0-8.0, mass volume ratio; Mixed solvent is by benzene: the volume ratio of ethanol=1: 1.5-4.0 is prepared.
Three (4-ethoxyl phenenyl) the bismuth purity that obtains with preparation method of the present invention reaches more than 99%, and productive rate is 80-85%, and fusing point is 72.4-74.1 ℃.
4-halogeno-benzene ether used in the present invention, Trichlorobismuthine all adopts the technical grade commercially available prod.
The present invention compared with prior art, the reaction conditions gentleness, the reaction times is short, simple and safe operation, good product quality has improved productive rate, has reduced cost, is suitable for suitability for industrialized production.
Specific implementation method
The invention will be further described below by embodiment, but embodiment does not limit protection scope of the present invention.
Embodiment 1
Having heating, stirring, in the 500ml four-hole boiling flask of thermometer, reflux condensing tube, drying tube, add 0.45mol (10.8g) magnesium powder respectively, 20ml tetrahydrofuran (THF) (THF), 0.3g monobromethane, import nitrogen, nitrogen atmosphere stirs down, adds the initiation reaction of 0.05g iodine, slowly splashes into the mixed solution of 0.4mol (62.7g) 4-chlorophenetole and 50ml THF in 1.5 hours, heat temperature raising reacted 5 hours to refluxing.Be cooled to room temperature, splash into the mixed solution of 0.13mol (41.2g) Trichlorobismuthine and 120ml THF in 1 hour, heat temperature raising is to refluxing, reacted 3 hours, be cooled to room temperature, reaction solution is poured in 200ml 15% hydrochloric acid soln, adds 100ml benzene and extracts, and the organic phase of telling washes with water to neutrality, anhydrous sodium sulfate drying, filter, filtrate steaming removal solvent obtains three (4-ethoxyl phenenyl) bismuth crude product, carry out recrystallization with 550ml benzene/alcohol mixed solvent (benzene and alcoholic acid volume ratio are 1: 2), obtain white three (4-ethoxyl phenenyl) bismuth 62.5g, productive rate 82%, purity 99.4% (HPLC).Fusing point 72.8-74.1 ℃.
Embodiment 2
Having heating, stirring, add 0.416mol (10g) magnesium powder in the 500ml four-hole boiling flask of thermometer, reflux condensing tube, drying tube respectively, 20ml tetrahydrofuran (THF) (THF), 0.5g N-PROPYLE BROMIDE imports nitrogen, nitrogen atmosphere stirs down, add the initiation reaction of 0.1g liquid bromine, slowly splash into the mixed solution of 0.4mol (80.4g) 4-Bromoethyl phenyl ether and 100ml THF in 1 hour, heat temperature raising reacted 3 hours to refluxing.Be cooled to room temperature, splash into the mixed solution of 0.12mol (38g) Trichlorobismuthine and 100ml THF in 40 minutes, heat temperature raising is to refluxing, reacted 2.5 hours, be cooled to room temperature, reaction solution is poured in 200ml 20% sulphuric acid soln, adds 100ml benzene and extracts, and the organic phase of telling washes with water to neutrality, anhydrous sodium sulfate drying, filter, filtrate steaming removal solvent obtains three (4-ethoxyl phenenyl) bismuth crude product, carry out recrystallization with 500ml benzene/alcohol mixed solvent (benzene and alcoholic acid volume ratio are 2: 3), obtain white three (4-ethoxyl phenenyl) bismuth 55g, productive rate 80%, purity 99.2% (HPLC).Fusing point 72.6-74.1 ℃.
Embodiment 3
Having heating, stirring, add 0.41mol (9.8g) magnesium powder in the 500ml four-hole boiling flask of thermometer, reflux condensing tube, drying tube respectively, 20ml tetrahydrofuran (THF) (THF), 0.4g monobromethane imports nitrogen, nitrogen atmosphere stirs down, add the initiation reaction of 0.05g iodine, 1.5 slowly splash into the mixed solution of 0.4mol (80.4g) 4-Bromoethyl phenyl ether and 120ml THF in hour, heat temperature raising reacted 4.5 hours to refluxing.Be cooled to room temperature, splash into the mixed solution of 0.13mol (41.2g) Trichlorobismuthine and 120ml THF in 40 minutes, heat temperature raising is to refluxing, reacted 1.5 hours, be cooled to room temperature, reaction solution is poured in 200ml 20% sulphuric acid soln, adds 150ml benzene and extracts, and the organic phase of telling washes with water to neutrality, anhydrous sodium sulfate drying, filter, filtrate steaming removal solvent obtains three (4-ethoxyl phenenyl) bismuth crude product, carry out recrystallization with 600ml benzene/alcohol mixed solvent (benzene and alcoholic acid volume ratio are 1: 4), obtain white three (4-ethoxyl phenenyl) bismuth 65g, productive rate 85%, purity 99.0% (HPLC).Fusing point 72.4-73.9 ℃.
Claims (8)
1. the preparation method of one kind three (4-ethoxyl phenenyl) bismuth comprises the steps:
(1) preparation of Grignard reagent: halogenated alkane, magnesium powder and tetrahydrofuran (THF) reaction solvent under nitrogen atmosphere, are added the elemental halogen initiation reaction, obtain Grignard reagent;
(2) 4-halogeno-benzene ether is dissolved in the tetrahydrofuran (THF) reaction solvent, splashes into step in 1-2 hour
(1) in the Grignard reagent, backflow 2-5 hour, reaction solution was cooled to room temperature;
(3) Trichlorobismuthine is dissolved in the tetrahydrofuran (THF) reaction solvent, is added dropwise to step in 0.5-1.5 hour
(2) in the reaction solution, backflow 1-3 hour, from reaction product, collect three (4-ethoxyl phenenyl) bismuth crude product then, the mixed solvent recrystallization with benzene and ethanol are formed obtains target product.
2. method according to claim 1 is characterized in that, said 4-halogeno-benzene ether is 4-chlorinated benzene ether, 4-bromobenzene ether or 4-phenyl-iodide ether.
3. method according to claim 1 is characterized in that, said halogenated alkane is chloric ethane, bromic ether, chloro-propane or bromo propane.
4. method according to claim 1 is characterized in that, said elemental halogen is simple substance bromine or iodine.
5. method according to claim 1 is characterized in that, the batching mol ratio of reactant is a 4-halogeno-benzene ether: magnesium powder: Trichlorobismuthine=1: 1-1.20: 0.28-0.34.
6. method according to claim 1 is characterized in that, the batching molecular volume of reaction solvent is than being 4-halogeno-benzene ether: tetrahydrofuran (THF)=1: 100-350, Trichlorobismuthine: tetrahydrofuran (THF)=1: 2.5-3.5, mass volume ratio.
7. method according to claim 1 is characterized in that, reaction product at room temperature adds inorganic acid solution, and with benzene extraction, washing, drying is filtered, and steaming desolventizes, and obtains crude product.
8. according to power method according to claim 7, it is characterized in that said inorganic acid solution is hydrochloric acid soln or sulphuric acid soln, its concentration is 15-30wt%.
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| KR101376860B1 (en) | 2011-12-28 | 2014-03-21 | 주식회사 두산 | Bismuth compound and organic electroluminescent device using the same |
| CN105131041B (en) * | 2015-09-15 | 2018-10-09 | 湖南大学 | A kind of catalytic applications in novel triphenyl organo-bismuth (V) composition catalyst and preparation method thereof and nitrogenous compound synthesis |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1177357A (en) * | 1995-01-26 | 1998-03-25 | 耐克麦德英梅金公司 | Bismuth compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1177357A (en) * | 1995-01-26 | 1998-03-25 | 耐克麦德英梅金公司 | Bismuth compound |
Non-Patent Citations (8)
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| 刑其毅等.《基础有机化学》上册 第二版.高等教育出版社,1993,158-159页. * |
| 刘训恩 等.《三苯基铋的合成研究及应用》.《北京理工大学学报》12 S1.1992,12(S1),16-21页. |
| 刘训恩 等.三－（乙氧基苯基）铋的合成及应用.《北京理工大学学报》15 6.1995,15(6),7-10页. |
| 刘训恩等.《三苯基铋的合成研究及应用》.《北京理工大学学报》12 S1.1992,12(S1),16-21页. * |
| 刘训恩等.三-(乙氧基苯基)铋的合成及应用.《北京理工大学学报》15 6.1995,15(6),7-10页. * |
| 李继忠.《三苯铋的合成》.《化学试剂》25 4.2003,25(4),249页. |
| 李继忠.《三苯铋的合成》.《化学试剂》25 4.2003,25(4),249页. * |
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