CN103936551A - 3-Bromobiphenyl preparation method - Google Patents
3-Bromobiphenyl preparation method Download PDFInfo
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Abstract
The invention discloses a 3-bromobiphenyl preparation method which is as follows: using biphenyl as a raw material, performing four steps of reaction of nitration, reduction, bromination and deamination, then extracting for separation to finally obtain 3-bromodiphenyl. The method is simple, and the product is easy to separate.
Description
Technical field
The invention belongs to the acyclic or isocyclic compound field in new material technology field, relate to particularly a kind of method of the 3-of preparation bromo biphenyl.
Background technology
3-bromo biphenyl is a kind of important industrial raw material, is also a kind of application organic synthesis intermediate very widely, and it is widely used in the field such as pharmacy, liquid crystal industry.In recent years, the export volume of China 3-bromo biphenyl increased day by day, and main exit object is some production of liquid crystal displays enterprises of Japan, Korea S, had brought a large amount of profits to our country.
The method of synthetic 3-bromo biphenyl is more, the method of current industrial comparative maturity and widespread use is taking m-bromoaniline as raw material, in hydrochloric acid or sulfuric acid, under the low temperature of 0～5 DEG C, carry out diazotization reaction with S-WAT, bromophenyl diazonium salt between generation, a bromophenyl diazonium salt reacts with benzene and obtains.This reaction is comparatively loaded down with trivial details, and in reaction, produces multi-products, to the separation difficulty of 3-bromo biphenyl.
Summary of the invention
The object of this invention is to provide a kind of easy method of preparing 3-bromo biphenyl.The method, taking biphenyl as raw material, by nitrated, reduction, bromo, deaminizating four-step reaction, then separates in the mode of extraction, finally obtains 3-bromo biphenyl.The method is simple, and product is easily separated.
A method of preparing 3-bromo biphenyl, comprises the following steps:
1) nitration reaction
Biphenyl is dissolved in organic solvent, drips wherein the mixing acid of nitric acid and sulfuric acid, under 55～60 DEG C of conditions, react;
After having reacted, water extraction, collects organic phase, obtains nitration product;
Wherein, the mol ratio of described biphenyl and nitric acid is 1:1～1.6, and wherein 1:1.2 is best proportion; Described organic solvent discord sulfuric acid or nitric acid reaction, and do not dissolve each other with water;
2) reduction reaction
Under agitation condition, Xiang Shuizhong adds iron powder and catalyzer, obtains iron powder mixed solution;
Nitration product is added drop-wise in iron powder mixed solution and is reacted; Optimum reacts under 60 DEG C of conditions;
After having reacted, alkalize, obtain reduzate;
Wherein, the mol ratio of described nitration product and iron powder is 1:1～10, and wherein 1:4 is best proportion; Described catalyzer is to help iron powder catalytic reduction;
3) bromo-reaction
Under agitation condition, in reduzate, add bromine, room temperature reaction;
After having reacted, water extraction, obtains bromination product;
Wherein, the mol ratio of described reduzate and bromine is 1:1～4, and wherein 1:1.26 is best proportion;
4) desamination reaction
Bromination product is added to the water, with adding concentrated hydrochloric acid in backward reaction system, under agitation condition, makes the bromo-derivative hydrochloride generating dissolve.Be cooled to 0 DEG C, obtain bromination product hydrochloride mixed solution;
Sodium Nitrite is added in bromination product hydrochloride mixed solution, and temperature is no more than under 5 DEG C of conditions reacts;
After having reacted, add wherein sodium hypophosphite, be stirred to and reacted;
Finally, be extracted with ethyl acetate, obtain 3-bromo biphenyl;
Wherein, the mol ratio of described bromination product, Sodium Nitrite and sodium hypophosphite is 1:1～1.5:5～15, and wherein 1:1.2:10.0 is optimum reaction condition.Herein, bromination product first reacts with concentrated hydrochloric acid and generates hydrochloride soluble in water, thereby ensures that reaction is homogeneous phase, so that reaction can be carried out smoothly.
In step 1), in the mixing acid of described nitric acid and sulfuric acid, nitric acid and sulfuric acid are that equal-volume mixes.In mixing acid, sulfuric acid plays activation nitric acid.
In step 1), described organic solvent is ethylene dichloride, chloroform, methylene dichloride etc.
In step 1), the consumption of organic solvent, only need meet biphenyl and all dissolve.The optimum amount of organic solvent can fully stir and dispel the heat when guarantee system reaction again for dissolving biphenyl.
Water extraction, washes cost minimum on the one hand, only has on the other hand water acid complete unreacted can be removed.After reaction finishes, can be first by reaction system cool to room temperature, water extraction more afterwards.
In order to calculate the output of nitration product (mixture of 4-nitrobiphenyl and 2 nitro biphenyl), to determine the charging capacity of next step each material, can first the organic solvent in the nitration product obtaining be removed, after weighing, again dissolve with organic solvent again.If adopt this kind of mode to process nitration product, the organic solvent that again dissolves nitration product need meet not and step 2) catalyst reaction, and and water do not dissolve each other.Available organic solvent has tetrahydrofuran (THF), ethylene dichloride, chloroform, methylene dichloride etc.Remove organic solvent and can take to rotate evaporate to dryness.
Step 2) in, the described material that helps iron powder catalytic reduction is hydrochloric acid or sulfuric acid, and in iron powder mixed solution, the amount ratio of water, iron powder, catalyzer is 50～200ml:10～20g:0.1～1g, and wherein, 100ml:14g:0.5g is optimal conditions.Adding wherein hydrochloric acid or sulfuric acid as catalyzer, is because if only have iron powder reducing react slow and often reduce not exclusively in system.
Step 2) in, described alkalization is to add basifier to alkalize in system, the add-on of basifier is identical with the add-on of catalyzer.Basifier is the alkaline matter that alkali, carbonate and other do not participate in reaction, can be sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood or sodium bicarbonate.The object of alkalization is in order to prevent that amino product from becoming hydrochloride or vitriol.Can first will after reaction system cool to room temperature, alkalize again, be more conducive to like this aftertreatment.
After alkalization, can, under agitation condition, in system, add organic solvent, filter the organic phase of collecting in filtrate, obtain reduzate.The object that adds organic solvent is to reduce the viscosity of reduzate, is so more conducive to aftertreatment.The organic solvent of this organic solvent and nitration product can be identical can be different, preferably identical to reclaim.In order to calculate the output of reduzate, to determine the charging capacity of next step each material, can first the organic solvent in the reduzate obtaining be boiled off, after weighing, again dissolve with organic solvent again.
In step 3), used water extracts several times, merges organic phase, removes organic solvent, obtains bromination product (mixture of the bromo-4-phenylaniline of 3-, the bromo-6-phenylaniline of 5-and the bromo-6-phenylaniline of 3-).Conventionally extraction 3 times.Water extraction, washes cost minimum on the one hand, only has on the other hand water can remove the acid generating in reaction.
In step 4), the consumption of water, only needs to meet and bromination product hydrochloride all can be dissolved.Optimum amount, for can either dissolve bromination product hydrochloride, also can fully stir and dispel the heat when guarantee system reaction.The used in amounts of concentrated hydrochloric acid is excessive.Preferably, the mol ratio of bromination product and concentrated hydrochloric acid is 1:10～25, and wherein optimal conditions is 1:20.Can be by the aqueous solution of Sodium Nitrite being added drop-wise in bromination product hydrochloride mixed solution, more convenient operation and reaction are more even like this.
Can be extracted with ethyl acetate several times, merge organic phase, remove organic solvent, obtain 3-bromo biphenyl.Conventionally extraction 3 times.
In whole reaction, the progressively disappearance that can utilize thin-layer chromatography (TLC detection) to observe raw material spot judges whether reaction completes.Without raw material point, reaction has been thought.
Synthetic route of the present invention is as follows:
1) nitration reaction
2) reduction reaction
3) bromo-reaction
4) desamination reaction
The invention has the advantages that:
Simple, cheap raw material biphenyl for the present invention, utilizes cheap reagent, should make 3-bromo biphenyl through classical inverse;
Front 3 step products therefroms can directly carry out next step reaction, and whole reaction is easy to operate and cost is low;
The various products that generate in whole reaction scheme in the end can change into 3-bromo biphenyl, have omitted loaded down with trivial details separating step, and efficiency is high.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1
A method of preparing 3-bromo biphenyl, comprises the following steps:
1) nitration reaction
100g (0.65mol) biphenyl is dissolved in 500mL ethylene dichloride and is added in 2L there-necked flask.Under agitation condition, by the nitration mixture preparing in advance, (52mL68% nitric acid mixes and is made into the 52mL vitriol oil, wherein containing HNO
30.78mol) be carefully added drop-wise in reaction system.Dropwise rear maintenance temperature of reaction 55-60 DEG C 3 hours.Be cooled to room temperature and add 400mL water to extract.Collect organic phase, revolve and boil off except ethylene dichloride.The dry nitration product 100g, productive rate 78% of obtaining.
2) reduction reaction
In 2L there-necked flask, add 800mL water, under agitation condition, add 112g(2mol) concentrated hydrochloric acid of iron powder and 4g37%.100g (0.5mol) nitration product is dissolved in to 200mL tetrahydrofuran (THF) and is added drop-wise in reaction system.Be heated to 60 DEG C and keep 3 hours.Being cooled to room temperature also alkalizes with the NaOH aqueous solution.Under agitation condition, add 300mL tetrahydrofuran (THF).Filter, filtrate is divided into water and organic phase.Collect organic phase and tetrahydrofuran (THF) is spin-dried for.Obtain reduzate 76g, productive rate: 90%.
3) bromo-reaction
In 500mL there-necked flask, add 31g(0.19mol) reduzate and 150mL ethylene dichloride, the careful 38.1g(0.24mol that drips under agitation condition) Br
2.Normal-temperature reaction 3h.Add 300mL water to extract.Merge organic phase.Revolve and steam desolventizing ethylene dichloride, obtain bromination product 30g(productive rate 65%).
4) desamination reaction
In 2L there-necked flask, add 400mL water and 60g(0.24mol) bromination product.Add 37%HCl500.0g(5mol).Under agitation condition, be cooled to 0 DEG C.To be dissolved with 20g(0.29mol) NaNO
2the aqueous solution be carefully added drop-wise in reaction system, ensure that temperature of reaction is no more than 5 DEG C and react 3h.Add subsequently 258g(2.43mol) sodium hypophosphite, reaction is stirred and is spent the night.Add the extraction of 300mL ethyl acetate.Merge organic phase, be spin-dried for solvent.Residuum carries out underpressure distillation, can obtain 43g the finished product (productive rate 78%).
The product obtaining is detected, and result is
1h-NMR(CDCl
3, ppm) and 7.23-7.70(m, 9H),
13c – NMR(CDCl
3, ppm) and 122.8,125.6,127.0,127.8,127.8,130.1,130.1,130.1,139.6,143.3.Prove that product is 3-bromo biphenyl.
Embodiment 2
A method of preparing 3-bromo biphenyl, comprises the following steps:
1) nitration reaction
Biphenyl is dissolved in organic solvent, drips wherein the mixing acid of nitric acid and sulfuric acid, under 55 DEG C of conditions, react;
After having reacted, water extraction, collects organic phase, obtains nitration product;
Wherein, the mol ratio of described biphenyl and nitric acid is 1:1; Described organic solvent discord sulfuric acid or nitric acid reaction, and do not dissolve each other with water;
2) reduction reaction
Under agitation condition, Xiang Shuizhong adds iron powder and catalyzer, obtains iron powder mixed solution;
Nitration product is added drop-wise in iron powder mixed solution and is reacted;
After having reacted, alkalize, obtain reduzate;
Wherein, the mol ratio of described nitration product and iron powder is 1:1; Described catalyzer is to help iron powder catalytic reduction;
3) bromo-reaction
Under agitation condition, in reduzate, add bromine, room temperature reaction;
After having reacted, water extraction, obtains bromination product;
Wherein, the mol ratio of described reduzate and bromine is 1:1;
4) desamination reaction
Bromination product is added to the water, in reaction system, adds concentrated hydrochloric acid, under agitation condition, make the bromo-derivative hydrochloride generating dissolve, be cooled to 0 DEG C, obtain bromination product hydrochloride mixed solution;
Sodium Nitrite is added in bromination product hydrochloride mixed solution, and temperature is no more than under 5 DEG C of conditions reacts;
After having reacted, add wherein sodium hypophosphite, be stirred to and reacted;
Finally, be extracted with ethyl acetate, obtain 3-bromo biphenyl;
Wherein, the mol ratio of described bromination product, Sodium Nitrite and sodium hypophosphite is 1:1:5.
Embodiment 3
A method of preparing 3-bromo biphenyl, comprises the following steps:
1) nitration reaction
Biphenyl is dissolved in organic solvent, drips wherein the mixing acid of nitric acid and sulfuric acid, under 60 DEG C of conditions, react;
After having reacted, water extraction, collects organic phase, obtains nitration product;
Wherein, the mol ratio of described biphenyl and nitric acid is 1:1.6; Described organic solvent discord sulfuric acid or nitric acid reaction, and do not dissolve each other with water;
2) reduction reaction
Under agitation condition, Xiang Shuizhong adds iron powder and catalyzer, obtains iron powder mixed solution;
Nitration product is added drop-wise in iron powder mixed solution and is reacted;
After having reacted, alkalize, obtain reduzate;
Wherein, the mol ratio of described nitration product and iron powder is 1:10; Described catalyzer is to help iron powder catalytic reduction;
3) bromo-reaction
Under agitation condition, in reduzate, add bromine, room temperature reaction;
After having reacted, water extraction, obtains bromination product;
Wherein, the mol ratio of described reduzate and bromine is 1:4;
4) desamination reaction
Bromination product is added to the water, in reaction system, adds concentrated hydrochloric acid, under agitation condition, make the bromo-derivative hydrochloride generating dissolve, be cooled to 0 DEG C, obtain bromination product hydrochloride mixed solution;
Sodium Nitrite is added in bromination product hydrochloride mixed solution, and temperature is no more than under 5 DEG C of conditions reacts;
After having reacted, add wherein sodium hypophosphite, be stirred to and reacted;
Finally, be extracted with ethyl acetate, obtain 3-bromo biphenyl;
Wherein, the mol ratio of described bromination product, Sodium Nitrite and sodium hypophosphite is 1:1.5:15.
Embodiment 4
With embodiment 2, wherein, in step 1), in the mixing acid of described nitric acid and sulfuric acid, nitric acid and sulfuric acid are that equal-volume mixes; Described organic solvent is ethylene dichloride.Step 2) in, described nitration product and iron powder mixed solution react under 60 DEG C of conditions; The material of described help iron powder catalytic reduction is hydrochloric acid; In iron powder mixed solution, the amount ratio of water, iron powder, catalyzer is 50ml:10g:0.1g; The add-on of described basifier is identical with the add-on of catalyzer; Described basifier is sodium hydroxide.In step 4), the mol ratio of bromination product and concentrated hydrochloric acid is 1:10.
Embodiment 5
With embodiment 2, wherein, in step 1), in the mixing acid of described nitric acid and sulfuric acid, nitric acid and sulfuric acid are that equal-volume mixes; Described organic solvent is chloroform.Step 2) in, described nitration product and iron powder mixed solution react under 60 DEG C of conditions; The material of described help iron powder catalytic reduction is sulfuric acid; In iron powder mixed solution, the amount ratio of water, iron powder, catalyzer is 200ml:20g:1g; The add-on of described basifier is identical with the add-on of catalyzer; Described basifier is potassium hydroxide.In step 4), the mol ratio of bromination product and concentrated hydrochloric acid is 1:25.
Embodiment 6
With embodiment 2, wherein, in step 1), in the mixing acid of described nitric acid and sulfuric acid, nitric acid and sulfuric acid are that equal-volume mixes; Described organic solvent is methylene dichloride.Step 2) in, described nitration product and iron powder mixed solution react under 60 DEG C of conditions; The material of described help iron powder catalytic reduction is hydrochloric acid; In iron powder mixed solution, the amount ratio of water, iron powder, catalyzer is 100ml:15g:0.7g; The add-on of described basifier is identical with the add-on of catalyzer; Described basifier is sodium carbonate.In step 4), the mol ratio of bromination product and concentrated hydrochloric acid is 1:15.
Embodiment 7
With embodiment 2, wherein, in step 1), the mol ratio of described biphenyl and nitric acid is 1:1.2; Step 2) in, the mol ratio of described nitration product and iron powder is 1:4; In step 3), the mol ratio of described reduzate and bromine is 1:1.26; In step 4), the mol ratio of described bromination product, Sodium Nitrite and sodium hypophosphite is 1:1.2:10.0, and described basifier is salt of wormwood.
Embodiment 8
With embodiment 2, wherein, described basifier is sodium bicarbonate.
The above embodiment of the present invention is only for example of the present invention is clearly described, not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give exhaustive to all embodiments.Everyly belong to apparent variation or the still row in protection scope of the present invention of variation that technical scheme of the present invention extends out.
Claims (10)
1. a method of preparing 3-bromo biphenyl, is characterized in that, comprises the following steps:
1) nitration reaction
Biphenyl is dissolved in organic solvent, drips wherein the mixing acid of nitric acid and sulfuric acid, under 55～60 DEG C of conditions, react;
After having reacted, water extraction, collects organic phase, obtains nitration product;
Wherein, the mol ratio of described biphenyl and nitric acid is 1:1～1.6; Described organic solvent discord sulfuric acid or nitric acid reaction, and do not dissolve each other with water;
2) reduction reaction
Under agitation condition, Xiang Shuizhong adds iron powder and catalyzer, obtains iron powder mixed solution;
Nitration product is added drop-wise in iron powder mixed solution and is reacted;
After having reacted, alkalize, obtain reduzate;
Wherein, the mol ratio of described nitration product and iron powder is 1:1～10; Described catalyzer is to help iron powder catalytic reduction;
3) bromo-reaction
Under agitation condition, in reduzate, add bromine, room temperature reaction;
After having reacted, water extraction, obtains bromination product;
Wherein, the mol ratio of described reduzate and bromine is 1:1～4;
4) desamination reaction
Bromination product is added to the water, in reaction system, adds concentrated hydrochloric acid, under agitation condition, make the bromo-derivative hydrochloride generating dissolve, be cooled to 0 DEG C, obtain bromination product hydrochloride mixed solution;
Sodium Nitrite is added in bromination product hydrochloride mixed solution, and temperature is no more than under 5 DEG C of conditions reacts;
After having reacted, add wherein sodium hypophosphite, be stirred to and reacted;
Finally, be extracted with ethyl acetate, obtain 3-bromo biphenyl;
Wherein, the mol ratio of described bromination product, Sodium Nitrite and sodium hypophosphite is 1:1～1.5:5～15.
2. the method for preparing 3-bromo biphenyl according to claim 1, is characterized in that, in step 1), in the mixing acid of described nitric acid and sulfuric acid, nitric acid and sulfuric acid are that equal-volume mixes; Described organic solvent is ethylene dichloride, chloroform, methylene dichloride.
3. the method for preparing 3-bromo biphenyl according to claim 1, is characterized in that step 2) in, described nitration product and iron powder mixed solution react under 60 DEG C of conditions.
4. the method for preparing 3-bromo biphenyl according to claim 1, is characterized in that step 2) in, the material of described help iron powder catalytic reduction is hydrochloric acid or sulfuric acid.
5. the method for preparing 3-bromo biphenyl according to claim 1, it is characterized in that, step 2) in, in iron powder mixed solution, the amount ratio of water, iron powder, catalyzer is 50～200ml:10～20g:0.1～1g, and more preferably in described iron powder mixed solution, the amount ratio of water, iron powder, catalyzer is 100ml:14g:0.5g.
6. the method for preparing 3-bromo biphenyl according to claim 1, is characterized in that step 2) in, described alkalization is to add basifier to alkalize in system, for alkali, carbonate and other do not participate in the alkaline matter of reaction.
7. the method for preparing 3-bromo biphenyl according to claim 1, is characterized in that step 2) in, the add-on of described basifier is identical with the add-on of catalyzer.
8. according to the method for preparing 3-bromo biphenyl described in claim 6 or 7, it is characterized in that, described basifier is sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood or sodium bicarbonate.
9. the method for preparing 3-bromo biphenyl according to claim 1, is characterized in that, in step 4), the mol ratio of bromination product and concentrated hydrochloric acid is 1:10～25, and more preferably the mol ratio of described bromination product and concentrated hydrochloric acid is 1:20.
10. the method for preparing 3-bromo biphenyl according to claim 1, is characterized in that, in step 1), the mol ratio of described biphenyl and nitric acid is 1:1.2; Step 2) in, the mol ratio of described nitration product and iron powder is 1:4; In step 3), the mol ratio of described reduzate and bromine is 1:1.26; In step 4), the mol ratio of described bromination product, Sodium Nitrite and sodium hypophosphite is 1:1.2:10.0.
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| CN201310021821.9A CN103936551B (en) | 2013-01-21 | 2013-01-21 | A kind of method preparing 3-bromo biphenyl |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108147946A (en) * | 2017-12-04 | 2018-06-12 | 华南农业大学 | A kind of method for preparing 4- phenylphenols |
| CN110028424A (en) * | 2019-05-15 | 2019-07-19 | 浙江长华科技股份有限公司 | Synthesis technology based on 2- amino -5- nitrobenzonitrile |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| GB2065655A (en) * | 1979-12-19 | 1981-07-01 | Upjohn Co | Preparing biphenyl compounds by coupling |
| US5254776A (en) * | 1992-07-17 | 1993-10-19 | Mallinckrodt Specialty Chemicals Company | Synthesis of bromobiphenyls |
-
2013
- 2013-01-21 CN CN201310021821.9A patent/CN103936551B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2065655A (en) * | 1979-12-19 | 1981-07-01 | Upjohn Co | Preparing biphenyl compounds by coupling |
| US5254776A (en) * | 1992-07-17 | 1993-10-19 | Mallinckrodt Specialty Chemicals Company | Synthesis of bromobiphenyls |
Non-Patent Citations (1)
| Title |
|---|
| W.FREDERICK HUBER ET AL.: "Vinyl Aromatic Compounds.II.o-,m- and p-Vinylbiphenyls", 《J.AMER.CHEM. SOC.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108147946A (en) * | 2017-12-04 | 2018-06-12 | 华南农业大学 | A kind of method for preparing 4- phenylphenols |
| CN110028424A (en) * | 2019-05-15 | 2019-07-19 | 浙江长华科技股份有限公司 | Synthesis technology based on 2- amino -5- nitrobenzonitrile |
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