CN101020694A - Industrial preparation method of triphenyl bismuth series compound - Google Patents
Industrial preparation method of triphenyl bismuth series compound Download PDFInfo
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- CN101020694A CN101020694A CN 200710020161 CN200710020161A CN101020694A CN 101020694 A CN101020694 A CN 101020694A CN 200710020161 CN200710020161 CN 200710020161 CN 200710020161 A CN200710020161 A CN 200710020161A CN 101020694 A CN101020694 A CN 101020694A
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Abstract
The invention discloses an industrial preparation method of triphenyl bismuth series compounds, which takes bromobenzene series compounds as raw materials, and carries out Grignard reaction with metal magnesium in an anhydrous solvent to generate an organic magnesium reagent, and then carries out reaction with anhydrous bismuth trichloride at the temperature of 20-120 ℃ to prepare the triphenyl bismuth series compounds, wherein the bromobenzene series compounds comprise bromobenzene, p-bromotoluene, m-bromotoluene and o-bromotoluene; the anhydrous solvent is one or a mixture of two or more solvents of tetrahydrofuran, benzene, toluene, ethylbenzene, p-xylene, o-xylene, m-xylene, N-methylpyrrolidone and the like; the reaction time is 2-24 hours; the organic solvent with higher boiling point is safer than ether and is beneficial to the activation of the metal magnesium chips; the method can be carried out under the anhydrous condition, the reaction condition is mild, no special requirement is required, and the yield is more than 90%.
Description
Technical field:
The present invention relates to the preparation method of triphenyl bismuth compounds, relate in particular to the industrialized process for preparing of triphenyl bismuth compounds.
Background technology:
Solid propellant is the important component part of rocket engine, its weight accounts for 90% of rocket engine gross weight, its expense accounts for space shuttle and always launches 20% of total cost, so the performance of solid propellant and cost play very great function to the development of aerospace industry.Bismuth organic compound is a combustioncatalysts important in the solid propellant, show after deliberation: organo-bismuth class propelling agent can solidify when room temperature, reduce the propellant curing temperature and can realize self-vulcanizing, minimizing and elimination propellant charge string stress, raising mechanical properties of propellant, minimizing energy consumption, reduction propelling agent cost, organo-bismuth class solid propellant is environmentally friendly solid propellant simultaneously, its toxicity is low, and characteristics such as excellent catalytic effect obtain wideling popularize of national governments.
At present bismuth organic compound mainly contains triphenyl bismuth compounds, as triphenyl bismuth, three (p-methylphenyl) bismuth), three (aminomethyl phenyl) bismuth, three (o-methyl-phenyl-) bismuths etc.Its synthetic method has a variety of, but most of, severe reaction conditions, and yield is low, is not suitable for suitability for industrialized production.
Existing preparation method one: adopt bromobenzene to generate lithium salts with the n-Butyl Lithium effect down, prepare triphenyl bismuth with anhydrous Trichlorobismuthine again at-78 ℃, this method condition harshness, the cost height have only laboratory study value, and yield has only 80%～81%.
Existing preparation method two: adopt bromobenzene and magnesium to react under anhydrous, anaerobic, nitrogen protection and generate phenyl-magnesium-bromide, with anhydrous Trichlorobismuthine prepared in reaction triphenyl bismuth, yield has only 75%～78% again, and this method can't be fit to suitability for industrialized production equally.
Summary of the invention:
In order to overcome the defective that exists among the existing preparation method, the invention provides a kind of industrialized process for preparing of triphenyl bismuth compounds, it has reaction conditions gentleness, easy and simple to handle, does not need nitrogen protection in the preparation process, and can suitability for industrialized production.
The present invention is a raw material with the bromobenzene series compound, carries out grignard reaction with MAGNESIUM METAL and generate organomagnesium reagent in anhydrous solvent, carries out the prepared in reaction triphenyl bismuth compounds with anhydrous Trichlorobismuthine under 20 ℃～120 ℃ conditions again, and reaction formula is as follows:
Described bromobenzene series compound comprises bromobenzene, para-bromo toluene, m-bromotoluene, o-bromotoluene; Described anhydrous solvent is the mixture of a kind of, two kinds or multiple solvent wherein such as tetrahydrofuran (THF), benzene, toluene, ethylbenzene, p-Xylol, o-Xylol, m-xylene, N-Methyl pyrrolidone; Described triphenyl bismuth compounds comprises triphenyl bismuth, three (p-methylphenyl) bismuth), three (aminomethyl phenyl) bismuth, three (o-methyl-phenyl-) bismuths; Reaction times is 2-24 hour.
Advantage of the present invention is:
1) organic solvent of employing higher such as tetrahydrofuran (THF), benzene, toluene, ethylbenzene, p-Xylol, o-Xylol, m-xylene, N-Methyl pyrrolidone geometric ratio are used ether safety, help the activation of metal magnesium chips simultaneously;
2) used anhydrous solvent is technical grade original packing product, does not need to carry out particular processing again;
3) under anhydrous condition, carry out, do not need complicated nitrogen protection device;
4) temperature of reaction is 20 ℃-120 ℃, does not need low temperature, and reaction conditions helps suitability for industrialized production;
5) reaction conditions gentleness, no particular requirement, yield is greater than 90%, and prior art only is about 80%.
Embodiment:
The preparation of example 1, triphenyl bismuth
In the reaction flask of 500L, add people's magnesium chips 6Kg, 0.2Kg iodine grain, 0.2Kg bromobenzene, 10L tetrahydrofuran (THF) and 30L toluene, be heated to 64 ℃, about 30 minutes of activation magnesium chips, drip the mixed solution of bromobenzene 38kg and 150L toluene, the control rate of addition is kept reaction solution and is slight boiling condition, after dropwising, reacted 5 hours down, make the magnesium chips effect complete at 65-75 ℃, be cooled to room temperature, under agitation add exsiccant Trichlorobismuthine 24.2Kg and 100L exsiccant toluene mixture adds the people in batches, after finishing, 110 ℃ of reactions 4 hours, after reaction finishes, cooling, the saturated aqueous solution stopped reaction with 10Kg ammonium chloride is made into extracts with toluene, recrystallization, filter, get oyster white crystallization triphenyl bismuth 30.1Kg after the drying, its productive rate is 91.7%, fusing point: 78 ℃～79 ℃ (literature value: 77 ℃～78 ℃).
The preparation of example 2, three (p-methylphenyl) bismuth
In the reaction flask of 500L, add people 6Kg, 0.2Kg iodine grain, 0.2Kg para-bromo toluene, 10L N-Methyl pyrrolidone and 30L benzene, be heated to 80 ℃ of activation magnesium chips about 30 minutes, be cooled to 20 ℃, at 20 ℃ of mixed solutions that drip para-bromo toluene 41.5Kg and 150L benzene down, the control rate of addition, temperature of reaction is controlled at about 20 ℃, after dropwising, continue to react 15 hours down, magnesium chips is reacted completely at 20 ℃.Under agitation add exsiccant Trichlorobismuthine 24.2Kg and 100L exsiccant benzol mixture adds the people in batches, after finishing, reacted 9 hours down at 80 ℃, after reaction finishes, cooling, the saturated aqueous solution stopped reaction that is made into 10Kg ammonium chloride, with getting white crystals three (p-methylphenyl) bismuth 34.2Kg after benzene extraction, recrystallization, filtration, the drying, its productive rate 92.4%, fusing point: 88 ℃～89 ℃, (literature value: 86 ℃～87 ℃).
The preparation of example 3, three (aminomethyl phenyl) bismuth
In the reaction flask of 500L, add people's magnesium chips 6.2Kg, 0.2Kg iodine grain, 0.2Kg m-bromotoluene, 10LN-methyl-2-pyrrolidone and 30L ethylbenzene, be heated to 120 ℃, about 30 minutes of activation magnesium chips, drip the mixed solution of m-bromotoluene 41.5Kg and 150L ethylbenzene, the control rate of addition is kept 120 ℃ of temperature of reaction, after dropwising, continue magnesium chips almost to be acted on fully 120 ℃ of reactions 1 hour, be cooled to room temperature, under agitation add exsiccant Trichlorobismuthine 24.2Kg and 100L exsiccant ethyl benzene mixtures adds the people in batches, after finishing, 120 ℃ of reactions 1 hour, after reaction finishes, cooling, the saturated aqueous solution stopped reaction with 10Kg ammonium chloride is made into extracts with ethylbenzene, recrystallization, filter, get white crystals three (aminomethyl phenyl) bismuth 34Kg after the drying, its productive rate 92.0%, fusing point: 78 ℃～79 ℃ (literature value: 78 ℃～79 ℃).
The preparation of example 4, three (o-methyl-phenyl-) bismuth
In the reaction flask of 500L, add people's magnesium chips 7Kg, 0.2Kg iodine grain, 0.2Kg o-bromotoluene, 40L toluene, heated 80 ℃ of activation magnesium chips about 30 minutes, drip the mixed solution of o-bromotoluene 41.5Kg and 150L toluene, temperature of reaction is controlled at about 80 ℃, after dropwising, continuation was reacted 8 hours down at 80 ℃, magnesium chips is reacted completely, be cooled to room temperature, under agitation add exsiccant Trichlorobismuthine 24.2Kg and 100L exsiccant toluene mixture adds the people in batches, after finishing, reacted 10 hours down at 80 ℃, after reaction finishes, cooling, the saturated aqueous solution stopped reaction that is made into 10Kg ammonium chloride, extract with toluene, recrystallization, filter, get white crystals three (o-methyl-phenyl-) bismuth 34.3Kg, its productive rate 92.8%, fusing point: 119 ℃～120 ℃ (literature value: 120 ℃～121 ℃) after the drying.
Claims (2)
1, the industrialized process for preparing of triphenyl bismuth compounds, it is characterized in that: with the bromobenzene series compound is raw material, in anhydrous solvent, carry out grignard reaction and generate organomagnesium reagent with MAGNESIUM METAL, carry out the prepared in reaction triphenyl bismuth compounds with anhydrous Trichlorobismuthine under 20 ℃～120 ℃ conditions again, reaction formula is as follows:
Described bromobenzene series compound comprises bromobenzene, para-bromo toluene, m-bromotoluene, o-bromotoluene; Described anhydrous solvent is any or two kinds wherein such as tetrahydrofuran (THF), benzene, toluene, ethylbenzene N-Methyl pyrrolidone or the mixture of multiple solvent; Described triphenyl bismuth compounds comprises triphenyl bismuth, three (p-methylphenyl) bismuth), three (aminomethyl phenyl) bismuth, three (o-methyl-phenyl-) bismuths; Reaction times is 2-24 hour.
2, according to the industrialized process for preparing of the described triphenyl bismuth compounds of claim 1, it is characterized in that: described anhydrous solvent is the mixture of tetrahydrofuran (THF) and toluene
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| CN 200710020161 CN101020694A (en) | 2007-02-23 | 2007-02-23 | Industrial preparation method of triphenyl bismuth series compound |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733154B (en) * | 2009-12-03 | 2012-04-04 | 苏州大学 | A kind of curing catalyst for solid propellant and preparation method thereof |
| CN105001258A (en) * | 2015-08-12 | 2015-10-28 | 黄石市利福达医药化工有限公司 | Preparation method for diphenylphosphinic acid |
| CN105131041A (en) * | 2015-09-15 | 2015-12-09 | 湖南大学 | Novel triphenyl organic bismuth (V) complex catalyst, preparation method thereof, and catalysis application thereof in nitrogen-containing compounds |
| CN111393481A (en) * | 2020-04-07 | 2020-07-10 | 上海拜乐新材料科技有限公司 | Preparation method of triphenyl bismuth diacid compound and application of triphenyl bismuth diacid compound in polyurethane |
| CN115260018A (en) * | 2022-10-08 | 2022-11-01 | 苏州源展材料科技有限公司 | Preparation method of tris (2, 6-tetramethyl-3, 5-pimelic acid) bismuth |
-
2007
- 2007-02-23 CN CN 200710020161 patent/CN101020694A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733154B (en) * | 2009-12-03 | 2012-04-04 | 苏州大学 | A kind of curing catalyst for solid propellant and preparation method thereof |
| CN105001258A (en) * | 2015-08-12 | 2015-10-28 | 黄石市利福达医药化工有限公司 | Preparation method for diphenylphosphinic acid |
| CN105131041A (en) * | 2015-09-15 | 2015-12-09 | 湖南大学 | Novel triphenyl organic bismuth (V) complex catalyst, preparation method thereof, and catalysis application thereof in nitrogen-containing compounds |
| 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 |
| CN111393481A (en) * | 2020-04-07 | 2020-07-10 | 上海拜乐新材料科技有限公司 | Preparation method of triphenyl bismuth diacid compound and application of triphenyl bismuth diacid compound in polyurethane |
| CN111393481B (en) * | 2020-04-07 | 2023-07-11 | 上海拜乐新材料科技有限公司 | Preparation method of triphenylbismuth diacid compound and application of triphenylbismuth diacid compound in polyurethane |
| CN115260018A (en) * | 2022-10-08 | 2022-11-01 | 苏州源展材料科技有限公司 | Preparation method of tris (2, 6-tetramethyl-3, 5-pimelic acid) bismuth |
| CN115260018B (en) * | 2022-10-08 | 2022-12-23 | 苏州源展材料科技有限公司 | Preparation method of tris (2,2,6,6-tetramethyl-3,5-pimelic acid) bismuth |
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Open date: 20070822 |