CN108863802A - A kind of preparation method of -4,4 '-dinitro biphenyl of 2,2 '-bis trifluoromethyl - Google Patents
A kind of preparation method of -4,4 '-dinitro biphenyl of 2,2 '-bis trifluoromethyl Download PDFInfo
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- CN108863802A CN108863802A CN201810878699.XA CN201810878699A CN108863802A CN 108863802 A CN108863802 A CN 108863802A CN 201810878699 A CN201810878699 A CN 201810878699A CN 108863802 A CN108863802 A CN 108863802A
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- bis trifluoromethyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/10—Preparation of nitro compounds by substitution of functional groups by nitro groups
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Abstract
The present invention provides a kind of 2,2 '-bis trifluoromethyl -4, the preparation method of 4 '-dinitro biphenyl includes the following steps：2,2 '-bis trifluoromethyl biphenyl of raw material is dissolved in N-Methyl pyrrolidone, and sulfonic acid chloride is then added dropwise at room temperature, after being added dropwise, nitrating agent is added portionwise in heating, until after raw material fully reacting, it is slowly added to ice water into reaction solution and is down to room temperature, with alkaline buffer solution tune PH to neutrality, oil reservoir is taken, after methanol eddy is added, slow cooling, 2,2 '-bis trifluoromethyl -4,4 '-dinitro biphenyl yellow solids are obtained by filtration after stirring.The present invention has many advantages, such as that reaction yield is higher, reaction condition is mild, post-processing is simple, good product quality using the method that ammonium nitrate is nitrified.
Description
Technical field
The present invention relates to diamine monomer 2,2 '-bis trifluoromethyl -4 that can be used as synthesis of polyimides liquid crystal material and use,
The preparation method of 4 '-benzidines.
Background technique
2,2 '--4,4 '-dinitro biphenyl of bis trifluoromethyl are to prepare liquid crystal material 2,2 '-bis trifluoromethyl -4,4 '-two
The important source material of aminobphenyl.2,2 '--4,4 '-dinitro biphenyl of bis trifluoromethyl add the methods of hydrogen or iron powder reducing through palladium carbon
2,2 '--4,4 '-benzidines of bis trifluoromethyl can be prepared after reduction nitro.2,2 '--4,4 '-diamino of bis trifluoromethyl connection
Benzene is a kind of important polyimide monomers material, is mainly used for flexible liquid crystal screen, electronic equipment transparent touch film, soft
The manufacture of property solar battery liner plate and flexible LED lighting apparatus, this new chemical materials are known as " Material Field solution by industry
The certainly expert of problem ", with excellent comprehensive such as high temperature resistant, high intensity, high insulation, low-k and low-dielectric loss
Can, it is widely used in high-technology field, is that the industries such as microelectronic component, wire and cable, computer and digital electrical apparatus can not
The key basic material of substitution.
At present using 2,2 '-bis trifluoromethyl -4,4 of nitrification process preparation '-dinitro biphenyl is reported in the literature has：
1) patent WO2008059724 is reacted 10 hours using the nitric acid concentrated sulfuric acid in methylene chloride, at 25-30 DEG C and is carried out
Nitration reaction generates 2,2 '-bis trifluoromethyl -4, and the conversion ratio of 4 '-dinitro biphenyl is 95.5%, yield 77%.
2) patent JP2008255037 equally uses nitration mixture for nitrating agent, small in 35 DEG C of reactions 6 in methylene chloride
When, 2,2 '-bis trifluoromethyl -4 are generated, 4 '-dinitro biphenyl conversion ratios are 87%, yield 76%.
3) patent JP2005126331 equally uses nitration mixture for nitrating agent, small in 40 DEG C or less reactions 8 in toluene
When, generate 2,2 '-bis trifluoromethyl -4,4 '-dinitro biphenyl, yield 91.5%.
4) patent JP03044355, using mixed acid nitrification, yield 86%.
5) patent CN104211944 is also using nitration mixture, and at room temperature, reaction obtains 2,2 '-under conditions of water as solvent
4,4 '-dinitro biphenyl of bis trifluoromethyl-, yield 66%.
Preparing nitrating agent used in the product using nitrification process in document at present is：Nitration mixture, i.e.,：Nitric acid/dense sulphur
Acid.It is lower that the product yield is prepared using nitrification process, and is easy to produce more nitro compounds, causes product separation difficult, furthermore
It is larger using nitration mixture risk.
Summary of the invention
In view of this, the present invention is directed to propose a kind of 2,2 '-bis trifluoromethyl -4, the preparation method of 4 '-dinitro biphenyl.
In order to achieve the above objectives, the technical proposal of the invention is realized in this way：2,2 '-bis trifluoromethyl -4,4 of one kind ' -
The preparation method of dinitro biphenyl, it is characterised in that：Include the following steps：Raw material 2,2 '-bis trifluoromethyl biphenyl is dissolved in N-
In methyl pyrrolidone, sulfonic acid chloride is then added dropwise at room temperature, after being added dropwise, nitrating agent is added portionwise in heating, until raw material
After fully reacting, ice water is slowly added into reaction solution and is down to room temperature, with alkaline buffer solution tune PH to neutrality, take oil reservoir, add
After entering methanol eddy, 2,2 '-bis trifluoromethyl -4,4 '-dinitro biphenyl yellow solids are obtained by filtration in slow cooling after stirring.
Reaction structure formula is as follows：
Preferably, the nitrating agent is one of potassium nitrate, sodium nitrite, copper nitrate or ammonium nitrate.
Preferably, the nitrating agent is ammonium nitrate.
Preferably, mole of 2, the 2 '-bis trifluoromethyl biphenyl, sulfonic acid chloride, N-Methyl pyrrolidone, nitrating agent
Proportion is 1：(1.4~2.2)：(5~9)：(2.5~3.5).
Preferably, mole of 2, the 2 '-bis trifluoromethyl biphenyl, sulfonic acid chloride, N-Methyl pyrrolidone, nitrating agent
Proportion is 1：1.8:7:3.
Preferably, the alkaline buffer solution is one in sodium carbonate liquor, sodium bicarbonate solution or solution of potassium carbonate
Kind.
Preferably, the alkaline buffer solution is sodium carbonate liquor.
Preferably, it is 35 DEG C -55 DEG C that temperature is warming up to after the addition sulfonic acid chloride.
Preferably, temperature 45 C is warming up to after the addition sulfonic acid chloride.
Preferably, the method that nitrating agent is added portionwise in the heating is to divide 3-5 batches nitrification is added in temperature-rise period
Reagent.
Preferably, the method that nitrating agent is added portionwise in the heating is point 4 batches of addition nitrification examinations in temperature-rise period
Agent.
It preferably, is 0.5-2 hours between the addition methanol eddy.
Preferably, the addition methanol eddy time is 1 hour.
Preferably, it is -10 DEG C -0 DEG C that temperature is cooled to after the addition methanol eddy.
Preferably, -5 DEG C of temperature are cooled to after the addition methanol eddy.
Preferably, the mixing time after the addition methanol eddy cooling is 0.5-2 hours.
Preferably, the mixing time after the addition methanol eddy cooling is 1 hour.
Compared with the existing technology, of the present invention a kind of 2,2 '-bis trifluoromethyl -4, the preparation of 4 '-dinitro biphenyl
Method has the advantage that：Using the method that ammonium nitrate is nitrified is higher with reaction yield, reaction condition is mild, post-processing
Simply, the advantages that good product quality.
Specific embodiment
In addition to being defined, technical term used in following embodiment has and the invention one of ordinary skill in the art
The identical meanings being commonly understood by.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；
The experimental method is unless otherwise specified conventional method.
Below with reference to embodiment, the present invention will be described in detail.
Embodiment 1
2,2 '-bis trifluoromethyl biphenyl of 14.5g and 34.5g N-Methyl pyrrolidone are added into reaction flask, stirs molten
12.1g sulfonic acid chloride is added dropwise after solution, after being added dropwise, is warming up to 45 DEG C or so, 12g ammonium nitrate is added portionwise, and (molar ratio is：2,
2 '-bis trifluoromethyl biphenyl：Sulfonic acid chloride：N-Methyl pyrrolidone：Ammonium nitrate=1：1.8：7：3), and keep anti-at a temperature of this
It answers, after TLC monitors raw material fully reacting, ice water is slowly added into reaction solution, with 5% sodium carbonate liquor tune PH to neutrality, is taken
Oil reservoir, after the reflux of 20 ml methanols being added 1 hour, after stirring 1 hour, 18.7g 2,2 '-is obtained by filtration to -5 DEG C in slow cooling
4,4 '-dinitro biphenyl yellow solid of bis trifluoromethyl-, yield 98.42%.
Embodiment 2
2,2 '-bis trifluoromethyl biphenyl of 14.5g and 25g N-Methyl pyrrolidone, stirring and dissolving are added into reaction flask
9.4g sulfonic acid chloride is added dropwise afterwards, after being added dropwise, is warming up to 35 DEG C or so, 9.6g ammonium nitrate is added portionwise, and (molar ratio is：2,2′-
Bis trifluoromethyl biphenyl：Sulfonic acid chloride：N-Methyl pyrrolidone：Ammonium nitrate=1：1.4：5：2.5) it, and keeps reacting at a temperature of this,
After TLC monitors raw material fully reacting, it is slowly added to ice water into reaction solution, with 5% sodium carbonate liquor tune PH to neutrality, takes oil
Layer, after the reflux of 20 ml methanols being added 1 hour, to -5 DEG C after stirring 1 hour, 17.3g 2 is obtained by filtration, 2 '-is bis- in slow cooling
4,4 '-dinitro biphenyl yellow solid of trifluoromethyl-, yield 91.05%.
Embodiment 3
2,2 '-bis trifluoromethyl biphenyl of 14.5g and 44.6g N-Methyl pyrrolidone are added into reaction flask, stirs molten
14.8g sulfonic acid chloride is added dropwise after solution, after being added dropwise, is warming up to 50 DEG C or so, 14g ammonium nitrate is added portionwise, and (molar ratio is：2,
2 '-bis trifluoromethyl biphenyl：Sulfonic acid chloride：N-Methyl pyrrolidone：Ammonium nitrate=1：2.2：9：3.5), and keep anti-at a temperature of this
It answers, after TLC monitors raw material fully reacting, ice water is slowly added into reaction solution, with 5% sodium carbonate liquor tune PH to neutrality, is taken
Oil reservoir, after the reflux of 20 ml methanols being added 1 hour, after stirring 1 hour, 18.8g 2,2 '-is obtained by filtration to -5 DEG C in slow cooling
4,4 '-dinitro biphenyl yellow solid of bis trifluoromethyl-, yield 98.94%.
Embodiment 4
2,2 '-bis trifluoromethyl biphenyl of 14.5g and 39.6g N-Methyl pyrrolidone are added into reaction flask, stirs molten
10.8g sulfonic acid chloride is added dropwise after solution, after being added dropwise, is warming up to 40 DEG C or so, 10.8g ammonium nitrate is added portionwise, and (molar ratio is：2,
2 '-bis trifluoromethyl biphenyl：Sulfonic acid chloride：N-Methyl pyrrolidone：Ammonium nitrate=1：1.6：6：2.7), and keep anti-at a temperature of this
It answers, after TLC monitors raw material fully reacting, ice water is slowly added into reaction solution, with 5% sodium carbonate liquor tune PH to neutrality, is taken
Oil reservoir, after the reflux of 20 ml methanols being added 1 hour, after stirring 1 hour, 18.2g 2,2 '-is obtained by filtration to -5 DEG C in slow cooling
4,4 '-dinitro biphenyl yellow solid of bis trifluoromethyl-, yield 95.78%.
Embodiment 5
2,2 '-bis trifluoromethyl biphenyl of 14.5g and 40g N-Methyl pyrrolidone, stirring and dissolving are added into reaction flask
10.8g sulfonic acid chloride is added dropwise afterwards, after being added dropwise, is warming up to 40 DEG C or so, 12.6g ammonium nitrate is added portionwise, and (molar ratio is：2,
2 '-bis trifluoromethyl biphenyl：Sulfonic acid chloride：N-Methyl pyrrolidone：Potassium nitrate=1：1.6：6：2.5), and keep anti-at a temperature of this
It answers, after TLC monitors raw material fully reacting, ice water is slowly added into reaction solution, with 5% solution of potassium carbonate tune PH to neutrality, is taken
Oil reservoir, after the reflux of 20 ml methanols being added 1 hour, after stirring 1 hour, 15.6g 2,2 '-is obtained by filtration to -5 DEG C in slow cooling
4,4 '-dinitro biphenyl yellow solid of bis trifluoromethyl-, yield 82.11%.
Embodiment 6
2,2 '-bis trifluoromethyl biphenyl of 14.5g and 40g N-Methyl pyrrolidone, stirring and dissolving are added into reaction flask
10.8g sulfonic acid chloride is added dropwise afterwards, after being added dropwise, is warming up to 40 DEG C or so, 10.4g sodium nitrite is added portionwise, and (molar ratio is：2,
2 '-bis trifluoromethyl biphenyl：Sulfonic acid chloride：N-Methyl pyrrolidone：Sodium nitrite=1：1.6：6：3), and keep anti-at a temperature of this
It answers, after TLC monitors raw material fully reacting, ice water is slowly added into reaction solution, with 5% sodium carbonate liquor tune PH to neutrality, is taken
Oil reservoir, after the reflux of 20 ml methanols being added 1 hour, after stirring 1 hour, 12.9g 2,2 '-is obtained by filtration to -5 DEG C in slow cooling
4,4 '-dinitro biphenyl yellow solid of bis trifluoromethyl-, yield 67.89%.
Embodiment 7
2,2 '-bis trifluoromethyl biphenyl of 14.5g and 65g N-Methyl pyrrolidone, stirring and dissolving are added into reaction flask
10.8g sulfonic acid chloride is added dropwise afterwards, after being added dropwise, is warming up to 40 DEG C or so, 23.3g copper nitrate is added portionwise, and (molar ratio is：2,
2 '-bis trifluoromethyl biphenyl：Sulfonic acid chloride：N-Methyl pyrrolidone：Copper nitrate=1：1.6：13：2.5), and at a temperature of keeping this
Reaction is slowly added to ice water into reaction solution, with 10% sodium bicarbonate solution tune PH into after TLC monitors raw material fully reacting
Property, oil reservoir is taken, after the reflux of 20 ml methanols being added 1 hour, slow cooling is to -5 DEG C, and after stirring 1 hour, 14.7g is obtained by filtration
2,2 '-bis trifluoromethyl -4,4 '-dinitro biphenyl yellow solids, yield 77.37%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. 2,2 '-bis trifluoromethyl -4 of one kind, the preparation method of 4 '-dinitro biphenyl, it is characterised in that：Include the following steps：
2,2 '-bis trifluoromethyl biphenyl of raw material is dissolved in N-Methyl pyrrolidone, and sulfonic acid chloride is then added dropwise at room temperature, is added dropwise
Afterwards, nitrating agent is added portionwise in heating, until being slowly added to ice water after raw material fully reacting into reaction solution and being down to room temperature, use alkali
Property buffer solution tune PH to neutrality, take oil reservoir, after methanol eddy is added, 2,2 '-bis- trifluoros are obtained by filtration in slow cooling after stirring
Methyl -4,4 '-dinitro biphenyl yellow solid.
2. according to claim 1 a kind of 2,2 '-bis trifluoromethyl -4, the preparation method of 4 '-dinitro biphenyl, feature
It is：The nitrating agent is one of potassium nitrate, sodium nitrite, copper nitrate or ammonium nitrate, preferably ammonium nitrate.
3. according to claim 1 a kind of 2,2 '-bis trifluoromethyl -4, the preparation method of 4 '-dinitro biphenyl, feature
It is：Described 2,2 '-bis trifluoromethyl biphenyl, sulfonic acid chloride, N-Methyl pyrrolidone, nitrating agent mol ratio be 1：
(1.4~2.2)：(5~9)：(2.5~3.5).
4. according to claim 1 or 3 a kind of 2,2 '-bis trifluoromethyl -4, the preparation method of 4 '-dinitro biphenyl,
It is characterized in that：Described 2,2 '-bis trifluoromethyl biphenyl, sulfonic acid chloride, N-Methyl pyrrolidone, nitrating agent mol ratio be
1：1.8:7:3.
5. according to claim 1 a kind of 2,2 '-bis trifluoromethyl -4, the preparation method of 4 '-dinitro biphenyl, feature
It is：The alkaline buffer solution is one of sodium carbonate liquor, sodium bicarbonate solution or solution of potassium carbonate, preferably carbonic acid
Sodium solution.
6. according to claim 1 a kind of 2,2 '-bis trifluoromethyl -4, the preparation method of 4 '-dinitro biphenyl, feature
It is：It is 35 DEG C -55 DEG C, preferably 45 DEG C that temperature is warming up to after the addition sulfonic acid chloride.
7. according to claim 1 a kind of 2,2 '-bis trifluoromethyl -4, the preparation method of 4 '-dinitro biphenyl, feature
It is：The method that nitrating agent is added portionwise in the heating is to divide 3-5 batches nitrating agent is added in temperature-rise period, is preferably existed
Point 4 batches of addition nitrating agents in temperature-rise period.
8. according to claim 1 a kind of 2,2 '-bis trifluoromethyl -4, the preparation method of 4 '-dinitro biphenyl, feature
It is：The addition methanol eddy time is 0.5-2 hours, preferably 1 hour.
9. according to claim 1 a kind of 2,2 '-bis trifluoromethyl -4, the preparation method of 4 '-dinitro biphenyl, feature
It is：It is -10 DEG C -0 DEG C, preferably -5 DEG C that temperature is cooled to after the addition methanol eddy.
10. according to claim 1 a kind of 2,2 '-bis trifluoromethyl -4, the preparation method of 4 '-dinitro biphenyl, spy
Sign is：Mixing time after the addition methanol eddy cooling is 0.5-2 hours, preferably 1 hour.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113045425A (en) * | 2021-03-18 | 2021-06-29 | 天津市泰合利华材料科技有限公司 | Method for preparing 2,2 '-bis (trifluoromethyl) -4, 4' -dinitrobiphenyl |
| CN114621111A (en) * | 2020-12-11 | 2022-06-14 | 李期林 | Mild synthesis method of 4-acetamido-5-nitro-m-xylene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114621111A (en) * | 2020-12-11 | 2022-06-14 | 李期林 | Mild synthesis method of 4-acetamido-5-nitro-m-xylene |
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