CN101357896A - 4-cyanobiphenyl preparation method - Google Patents
4-cyanobiphenyl preparation method Download PDFInfo
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- CN101357896A CN101357896A CNA2008101370072A CN200810137007A CN101357896A CN 101357896 A CN101357896 A CN 101357896A CN A2008101370072 A CNA2008101370072 A CN A2008101370072A CN 200810137007 A CN200810137007 A CN 200810137007A CN 101357896 A CN101357896 A CN 101357896A
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Abstract
The invention provides a preparation method for 4-cyanogen biphenyl, solves the problems of present preparation methods that the raw material has high toxicity, and the present method has high requirements of reaction conditions and is not suitable for industrial production. The method is characterized by comprising the following aspects: a. the synthesis of dibenzoyl chloride: dibenzoyl reacts with an acyl chlorinating agent to generate the dibenzoyl chloride; b. the preparation of biphenyl acyl amine: the dibenzoyl chloride reacts with ammonia gas to generate the biphenyl acyl amine; c. the preparation of the 4-cyano biphenyl: the biphenyl acyl amine reacts with a dehydrating agent, and colored impurities can be removed by petroleum ether and activated carbon, thus obtaining the 4-cyanogen biphenyl with purity of more than 99 percent. The method is characterized by low toxicity of the raw material, uneasy environmental pollution and easy storage; the production conditions are easily to be achieved and the process is easy to be controlled; the purity of the 4-cyanogen biphenyl prepared can reach more than 99 percent and the method is suitable for industrial production.
Description
Technical field
The invention belongs to the organic compound preparation field, be specifically related to a kind of preparation method of liquid crystal material intermediate 4-cyanobiphenyl.
Background technology
The 4-cyanobiphenyl is a kind of important liquid crystal material intermediate, can be widely used in fields such as medicine, dyestuff.The preparation method of relevant 4-cyanobiphenyl discloses a kind of preparation method abroad: with the biphenyl bromination, obtain 4-bromo biphenyl and by product 4 with the liquid bromine, the mixture of 4-'-dibromobiphenyl, underpressure distillation obtains the 4-bromo biphenyl, with 4-bromo biphenyl and cupric cyanide reaction, makes the 4-cyanobiphenyl again.The used liquid bromine of this method has extremely strong toxic and corrodibility to human body, and volatile, the seal request of preparation process is very strict, in case cause leakage, will pollute environment, if sucked by human body, then can stimulating mucosal, cause symptoms such as cough, headache, nasal bleeding, also can cause when concentration is higher and suffocate, workers'health is worked the mischief, and the difficult storage of liquid bromine, should handle by the oxidisability reagent requirement again by corrosive reagents; Used cupric cyanide also has severe toxicity in the reaction; This method is unsuitable for suitability for industrialized production in sum.The preparation method of external disclosed another kind of 4-cyanobiphenyl, it mainly is to adopt biphenyl, mauguinite and aluminum trichloride (anhydrous) reaction to make the 4-cyanobiphenyl.Its main raw material mauguinite has severe toxicity, eye and respiratory tract there is the strong impulse effect, lower concentration promptly has the strong stimulation effect to respiratory tract and eye, during high density, cause dizzy, nauseating, shed tears in a large number, cough, expiratory dyspnea, pulmonary edema even dead rapidly, so want strict seal in the preparation process, once cause leakage, will pollute environment, human body is worked the mischief; This method is unsuitable for suitability for industrialized production.
Summary of the invention
The objective of the invention is for solve the existing method that prepare the 4-cyanobiphenyl exist the raw material toxic greatly, reaction conditions requires height, is unsuitable for the problem of suitability for industrialized production, and provides a kind of preparation method of 4-cyanobiphenyl.
The preparation method's of 4-cyanobiphenyl of the present invention step is as follows: a, biphenyl mixed and stir by mass ratio 1: 2～2.5 with the solvent of chlorobenzene or dichlorobenzene biphenyl is dissolved fully, the catalyzer aluminum trichloride (anhydrous) that adds 1～1.3 times of biphenyl mole number, drip the acyl chlorinating agent of 0.9～1.3 times of biphenyl mole number again and make the temperature of solution remain 20～35 ℃, carry out liquid chromatographic detection every 20～30min sampling, when biphenyl content is lower than 5% in the reaction solution, pour in the mixture of ice and water reaction solution and stirring, treat to get organic phase after the layering, repeat again to wash 2～3 times, obtain yellow powder behind the suction filtration; B, the solvent of above-mentioned yellow powder and chlorobenzene or tetrahydrofuran (THF) is mixed and stirring and dissolving by mass ratio 1: 4～6, speed with 0.035～0.092mol/min under the normal temperature feeds ammonia in solution, carry out liquid chromatographic detection every 15～20min sampling, when being lower than 3%, the content of biphenyl acyl chlorides stops to feed ammonia, solution left standstill 3～5 hours obtains white powder behind the suction filtration; C, the solvent of above-mentioned white powder and chlorobenzene or ethylene dichloride is mixed and stirring and dissolving by mass ratio 1: 4～6, the dewatering agent that adds 2～4 times of biphenyl acid amides quality again, with solution heat temperature raising to 70 ℃, constant temperature refluxed 14～16 hours, normal pressure is distillation evaporate to dryness reaction solution down, adds the sherwood oil of 8～10 times of biphenyl acid amides quality and the gac of biphenyl acid amides quality 3～5%, is heated to 90～120 ℃ and keeps 0.5～1 hour, stir cooling behind the heat filtering, obtain off-white powder behind the suction filtration.
The first step of the present invention is the synthetic of biphenyl acyl chlorides, its reactant is biphenyl and acyl chlorinating agent, wherein acyl chlorinating agent is dichloroacetyl chloride or trichoroacetic chloride, used catalyzer is an aluminum trichloride (anhydrous) in the reaction, the biphenyl acyl chlorides that this reaction generates is two chloracetyl biphenyl or tribromo-acetyl biphenyl, and concrete reaction equation is as follows:
After reaction is finished, reaction solution with mixture of ice and water washing 3～4 times, is removed aluminum chloride wherein.
Second step was that the preparation of biphenyl acid amides, reactant were the biphenyl acyl chlorides that ammonia and the first step reaction make, and concrete reaction equation is as follows:
The 3rd step was that the preparation of 4-cyanobiphenyl, reactant were the biphenyl acid amides that dewatering agent and the reaction of second step make, and wherein dewatering agent is sulfur oxychloride or phosphorus oxychloride, and concrete reaction equation is as follows:
Prepared after reaction is finished is 4-cyanobiphenyl crude product, behind sherwood oil and gac removal foreign pigment wherein, can obtain the 4-cyanobiphenyl pure product of purity more than 99%.
The present invention has following beneficial effect: raw materials such as used biphenyl, acyl chlorinating agent and dewatering agent are with respect to liquid bromine and prussiate, and are little to the toxic of human body, be difficult for environment is polluted and be easy to store; The temperature of whole process of preparation is controlled in 120 ℃, produces required temperature condition and is easy to reach; Preparation process does not require strict air-proof condition, and preparation process is easy to control; The purity height of prepared 4-cyanobiphenyl can reach more than 99%, is suitable for suitability for industrialized production.
Embodiment
The invention will be further described below in conjunction with embodiment:
The preparation method's of this 4-cyanobiphenyl step is as follows: a, biphenyl mixed and stir by mass ratio 1: 2～2.5 with the solvent of chlorobenzene or dichlorobenzene biphenyl is dissolved fully, the catalyzer aluminum trichloride (anhydrous) that adds 1～1.3 times of biphenyl mole number, drip the acyl chlorinating agent of 0.9～1.3 times of biphenyl mole number again and make the temperature of solution remain 20～35 ℃, carry out liquid chromatographic detection every 20～30min sampling, when biphenyl content is lower than 5% in the reaction solution, pour in the mixture of ice and water reaction solution and stirring, treat to get organic phase after the layering, repeat again to wash 2～3 times, obtain yellow powder behind the suction filtration; B, the solvent of above-mentioned yellow powder and chlorobenzene or tetrahydrofuran (THF) is mixed and stirring and dissolving by mass ratio 1: 4～6, speed with 0.035～0.092mol/min under the normal temperature feeds ammonia in solution, carry out liquid chromatographic detection every 15～20min sampling, when being lower than 3%, the content of biphenyl acyl chlorides stops to feed ammonia, solution left standstill 3～5 hours obtains white powder behind the suction filtration; C, the solvent of above-mentioned white powder and chlorobenzene or ethylene dichloride is mixed and stirring and dissolving by mass ratio 1: 4～6, the dewatering agent that adds 2～4 times of biphenyl acid amides quality again, with solution heat temperature raising to 70 ℃, constant temperature refluxed 14～16 hours, normal pressure is distillation evaporate to dryness reaction solution down, adds the sherwood oil of 8～10 times of biphenyl acid amides quality and the gac of biphenyl acid amides quality 3～5%, is heated to 90～120 ℃ and keeps 0.5～1 hour, stir cooling behind the heat filtering, obtain off-white powder behind the suction filtration; Wherein tetrahydrofuran (THF) can be by 1, the 4-dioxane substitutes.
The first step of the present invention is the synthetic of biphenyl acyl chlorides, its reactant is biphenyl and acyl chlorinating agent, wherein acyl chlorinating agent is dichloroacetyl chloride or trichoroacetic chloride, used catalyzer is an aluminum trichloride (anhydrous) in the reaction, the biphenyl acyl chlorides that this reaction generates is two chloracetyl biphenyl or tribromo-acetyl biphenyl, and concrete reaction equation is as follows:
After reaction is finished, reaction solution with mixture of ice and water washing 3～4 times, is removed aluminum chloride wherein.
Second step was that the preparation of biphenyl acid amides, reactant were the biphenyl acyl chlorides that ammonia and the first step reaction make, and concrete reaction equation is as follows:
The 3rd step was that the preparation of 4-cyanobiphenyl, reactant were the biphenyl acid amides that dewatering agent and the reaction of second step make, and wherein dewatering agent is sulfur oxychloride or phosphorus oxychloride, and concrete reaction equation is as follows:
Prepared after reaction is finished is 4-cyanobiphenyl crude product, behind sherwood oil and gac removal foreign pigment wherein, can obtain the 4-cyanobiphenyl pure product of purity more than 99%.
Embodiment one: a, put into 300g biphenyl and 600g chlorobenzene in the reaction vessel and stir and make the biphenyl dissolving, add the 338g aluminum trichloride (anhydrous), drip the 373g dichloroacetyl chloride again, and by water-bath control solution temperature at 20～30 ℃, carry out liquid chromatographic detection every the 20min sampling, biphenyl content in reaction solution is lower than 5%, pour into reaction solution in the 1000ml mixture of ice and water and stir this moment, treat to get organic phase after the layering, repeat again to wash 2 times, obtain yellow powder behind the suction filtration, be weighed as 370g; B, above-mentioned yellow powder joined in the chlorobenzene of 2220g and stirring and dissolving, speed with 0.035～0.050mol/min under the normal temperature feeds ammonia in solution, carry out liquid chromatographic detection every the 15min sampling, the content of biphenyl acyl chlorides is less than 3% in solvent, stop to feed ammonia this moment, with solution left standstill 4 hours, suction filtration obtained white powder then, is weighed as 235g; C, above-mentioned white powder is joined in the 1410g chlorobenzene and stirring and dissolving, add dewatering agent sulfur oxychloride 940g again, with solution heat temperature raising to 70 ℃, constant temperature refluxed 14 hours, normal pressure is distillation evaporate to dryness reaction solution down, add 2350g sherwood oil and 11.7g gac, be heated to 90 ℃ and kept 0.5 hour, stir cooling behind the heat filtering, suction filtration obtains off-white powder 4-cyanobiphenyl, be weighed as 180g, through liquid chromatographic detection, its purity is 99.2%.
Embodiment two: a, the dichlorobenzene of 30g biphenyl and 75g put in the reaction vessel and stir make the biphenyl dissolving, add the 23.4g aluminum trichloride (anhydrous), Dropwise 35 .5g trichoroacetic chloride again, and by water-bath control solution temperature at 25～35 ℃, detect every 30min sampling carrying out liquid chromatography, biphenyl content in reaction solution is lower than 5%, pour into reaction solution in the 100ml mixture of ice and water and stir this moment, treat to get organic phase after the layering, repeat again to wash 3 times, obtain yellow powder behind the suction filtration, be weighed as 32g; B, with above-mentioned yellow powder join 128g 1, in the 4-dioxane and stirring and dissolving, speed with 0.075～0.092mol/min under the normal temperature feeds ammonia in solution, carry out liquid chromatographic detection every the 20min sampling, when the content of biphenyl acyl chlorides less than 3%, stop to feed ammonia this moment, with solution left standstill 5 hours, suction filtration obtained white powder then, is weighed as 25g; C, above-mentioned white powder joined in the ethylene dichloride of 100g and stirring and dissolving, add dewatering agent sulfur oxychloride 50g again, during with solution heat temperature raising to 70 ℃, constant temperature refluxed 16 hours, normal pressure is distillation evaporate to dryness reaction solution down, add 200g sherwood oil and 0.75g gac, be heated to 120 ℃ and kept 0.8 hour, stir cooling behind the heat filtering, suction filtration obtains off-white powder 4-cyanobiphenyl, be weighed as 18.5g, through liquid chromatographic detection, its purity is 99.4%.
Embodiment three: a, the chlorobenzene of 300g biphenyl and 700g put in the reaction vessel and stir make the biphenyl dissolving, add the 330g aluminum trichloride (anhydrous), drip the 370g dichloroacetyl chloride again, and by water-bath control solution temperature at 25～30 ℃, carry out liquid chromatographic detection every the 25min sampling, biphenyl content in reaction solution is lower than 5%, pour into reaction solution in the 1000ml mixture of ice and water and stir this moment, treat to get organic phase after the layering, repeat again to wash 2 times, obtain yellow powder behind the suction filtration, be weighed as 360g; B, above-mentioned yellow powder joined in the tetrahydrofuran (THF) of 2500g and stirring and dissolving, speed with 0.055～0.080mol/min under the normal temperature feeds ammonia in solution, carry out liquid chromatographic detection every the 18min sampling, when the content of biphenyl acyl chlorides less than 3%, stop to feed ammonia this moment, with solution left standstill 3 hours, suction filtration obtained white powder then, is weighed as 250g; C, above-mentioned white powder joined in the chlorobenzene of 980g and stirring and dissolving, add dewatering agent 1000g phosphorus oxychloride again, during with solution heat temperature raising to 70 ℃, constant temperature refluxed 15 hours, normal pressure is distillation evaporate to dryness reaction solution down, add 2000g sherwood oil and 10g gac, be heated to 100 ℃ and kept 1 hour, stir cooling behind the heat filtering, suction filtration obtains off-white powder 4-cyanobiphenyl, be weighed as 192g, through liquid chromatographic detection, its purity is 99.3%.
Claims (4)
1, a kind of preparation method of 4-cyanobiphenyl is characterized in that this preparation method's step is as follows:
A, biphenyl mixed and stir by mass ratio 1: 2～2.5 with the solvent of chlorobenzene or dichlorobenzene biphenyl is dissolved fully, the catalyzer aluminum trichloride (anhydrous) that adds 1～1.3 times of biphenyl mole number, drip the acyl chlorinating agent of 0.9～1.3 times of biphenyl mole number again and make the temperature of solution remain 20～35 ℃, carry out liquid chromatographic detection every 20～30min sampling, when biphenyl content is lower than 5% in the reaction solution, pour in the mixture of ice and water reaction solution and stirring, treat to get organic phase after the layering, repeat again to wash 2～3 times, obtain yellow powder behind the suction filtration;
B, the solvent of above-mentioned yellow powder and chlorobenzene or tetrahydrofuran (THF) is mixed and stirring and dissolving by mass ratio 1: 4～6, speed with 0.035～0.092mol/min under the normal temperature feeds ammonia in solution, carry out liquid chromatographic detection every 15～20min sampling, when being lower than 3%, the content of biphenyl acyl chlorides stops to feed ammonia, solution left standstill 3～5 hours obtains white powder behind the suction filtration;
C, the solvent of above-mentioned white powder and chlorobenzene or ethylene dichloride is mixed and stirring and dissolving by mass ratio 1: 4～6, the dewatering agent that adds 2～4 times of biphenyl acid amides quality again, with solution heat temperature raising to 70 ℃, constant temperature refluxed 14～16 hours, normal pressure is distillation evaporate to dryness reaction solution down, adds the sherwood oil of 8～10 times of biphenyl acid amides quality and the gac of biphenyl acid amides quality 3～5%, is heated to 90～120 ℃ and keeps 0.5～1 hour, stir cooling behind the heat filtering, obtain off-white powder behind the suction filtration.
2, the preparation method of a kind of 4-cyanobiphenyl according to claim 1 is characterized in that: described tetrahydrofuran (THF) can be by 1, the 4-dioxane substitutes.
3, the preparation method of a kind of 4-cyanobiphenyl according to claim 1 is characterized in that: described acyl chlorinating agent is dichloroacetyl chloride or trichoroacetic chloride.
4, the preparation method of a kind of 4-cyanobiphenyl according to claim 1 is characterized in that: described dewatering agent is sulfur oxychloride or phosphorus oxychloride.
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| CNA2008101370072A CN101357896A (en) | 2008-08-27 | 2008-08-27 | 4-cyanobiphenyl preparation method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503855A (en) * | 2011-12-09 | 2012-06-20 | 华东理工大学 | Synthetic method of 4-cyanobiphenyl |
| CN102633685A (en) * | 2012-03-28 | 2012-08-15 | 林东翰 | P-phenyl cyanophenyl synthesis method |
| CN102925122A (en) * | 2012-11-22 | 2013-02-13 | 黄文章 | Synthesis method of humic amide used for oil-based drilling fluid |
| CN103012203A (en) * | 2012-12-11 | 2013-04-03 | 百合花集团有限公司 | Improved method for preparing 4-phenyl-cyanophenyl |
-
2008
- 2008-08-27 CN CNA2008101370072A patent/CN101357896A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503855A (en) * | 2011-12-09 | 2012-06-20 | 华东理工大学 | Synthetic method of 4-cyanobiphenyl |
| CN102633685A (en) * | 2012-03-28 | 2012-08-15 | 林东翰 | P-phenyl cyanophenyl synthesis method |
| CN102633685B (en) * | 2012-03-28 | 2015-04-08 | 湖北东奥化工科技有限公司 | P-phenyl cyanophenyl synthesis method |
| CN102925122A (en) * | 2012-11-22 | 2013-02-13 | 黄文章 | Synthesis method of humic amide used for oil-based drilling fluid |
| CN103012203A (en) * | 2012-12-11 | 2013-04-03 | 百合花集团有限公司 | Improved method for preparing 4-phenyl-cyanophenyl |
| CN103012203B (en) * | 2012-12-11 | 2014-12-24 | 百合花集团股份有限公司 | Improved method for preparing 4-phenyl-cyanophenyl |
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