CN101817729A - Preparation method of 3,5-difluoro-4-(2,2,2-trifluoroethoxyl) bromobenzene - Google Patents
Preparation method of 3,5-difluoro-4-(2,2,2-trifluoroethoxyl) bromobenzene Download PDFInfo
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Abstract
The invention relates to the field of liquid crystal intermediates of electronic materials, in particular to a preparation method of 3,5-difluoro-4-(2,2,2-trifluoroethoxyl) bromobenzene of a fluorinated liquid crystal intermediate. The method comprises the following steps of: carrying out etherification reaction on 3,45-trifluoronitrobenzene as a raw material to prepare 3,5-difluoro-4-(2,2,2-trifluoroethoxyl) nitrobenzene, and then carrying out reduction reaction, diazotization reaction and bromination reaction to generate the 3,5-difluoro-4-(2,2,2-trifluoroethoxyl) bromobenzene. The preparation method of the 3,5-difluoro-4-(2,2,2-trifluoroethoxyl) bromobenzene has available raw material, mild reaction condition, high safety coefficient and strong operability; the process is simple and is easy to realize industrialization; moreover, the product has high purity and stable quality and completely meets the operating requirements of serving as the liquid crystal intermediate.
Description
Technical field
The present invention relates to TFT liquid crystal intermediates preparation method's technical field.
Background technology
3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) bromobenzene is the long carbochain liquid crystalline cpd of polyfluoro, the fluorine atom contained because of trifluoro ethoxy in its structure replaces hydrogen atom, with respect to other groups, on volume near hydrogen atom, can not influence the ordered arrangement of liquid crystal because of steric effect, fluorine atom has higher electronegativity simultaneously, can guarantee that the fluorinated liquid crystal structure still has certain dipole moment, in addition the fat-soluble solvability that can make the fluorine-containing compound of end and side chain in the mixed liquid crystal prescription, can obviously increase other liquid crystal compositions again of fluorine.Therefore, 3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) bromobenzene is specially adapted to the prescription of mixed liquid crystal, this product is mixed use with low viscosity and high dielectric anisotropy nematic liquid crystalline material, can increase the dipole moment of molecule, reduce the time of response, improve the display performance of liquid crystal material, promote clearness, production high-performance liquid crystal material is had great importance.
At present, at home and abroad there is no about synthesizing 3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) report of bromobenzene, my company uses the research and development advantage, has formulated two research and development routes, and wherein a route adopts with 2, the 6-difluorophenol is a raw material, and through bromo, condensation can obtain product.This raw materials technology 2,6-difluorophenol price is higher, and yield is lower, and Atom economy is poor, and environment is unfriendly.And with 3,4, the 5-trifluoronitrobenzene is a raw material, through etherificate, hydrogenating reduction, diazotization again, bromination obtains 3, the preparation method of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) bromobenzene, not only yield rises significantly, and the low usage quantity of etherification reaction solvent pollutes for low, less energy-consumption, and the suitability for industrialized production of high yield provides possibility.
Summary of the invention
It is simple to the objective of the invention is to obtain a kind of technology that can provide, mild condition, environmental friendliness, the preparation 3 that Atom economy is high, the variation route of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) bromobenzene, novel method.
The invention provides a kind ofly 3, the preparation method of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) bromobenzene is to realize by following reaction:
Concrete steps are:
(1) 3,4,5-trifluoronitrobenzene and etherifying agent react, and generate 3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) oil of mirbane;
The reduction reaction takes place and generates 3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) aniline in (2) 3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) oil of mirbane under the effect of reductive agent;
(3) 3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) aniline carries out diazotization reaction under the effect of diazo reagent, the diazotization reaction product generates 3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) bromobenzene with the cuprous bromide reaction again.
Wherein the etherifying agent that uses in the step (1) is the trifluoroethanol solution of alkali, perhaps etherifying agent is a kind of and trifluoroethanol, the N in trifluoroethanol potassium, trifluoroethanol sodium or the trifluoroethanol lithium, dinethylformamide, 1, a kind of mixture in 3-dimethyl-2-imidazolone or the tetramethylene sulfone;
Reductive agent in the step (2) is hydrogen or iron powder;
Diazo reagent in the step (3) is Sodium Nitrite and sour mixed solution.
As one embodiment of the invention, the described etherifying agent of step (1) is the trifluoroethanol solution of alkali, and described alkali is potassium hydroxide, sodium hydroxide, calcium hydroxide, lithium hydroxide, preferred potassium hydroxide; 3,4, the mol ratio of 5-trifluoronitrobenzene and trifluoroethanol, alkali is 1: (1～5): (0.1～2), preferred 1: (2.5～3.5): (0.8～1.5).
As one embodiment of the invention, the described etherifying agent of step (1) is a kind of and trifluoroethanol, the N in trifluoroethanol potassium, trifluoroethanol sodium or the trifluoroethanol lithium, dinethylformamide, 1, a kind of mixture in 3-dimethyl-2-imidazolone or the tetramethylene sulfone, and 3,4, the mol ratio of 5-trifluoronitrobenzene and trifluoroethanol potassium, trifluoroethanol sodium or trifluoroethanol lithium is 1: (0.5～2), preferred 1: (0.8～1.5); 3,4,5-trifluoronitrobenzene and trifluoroethanol, N, dinethylformamide, 1, a kind of mass ratio in 3-dimethyl-2-imidazolone or the tetramethylene sulfone is 1: (1～5), preferred 1: (3～4).
As a preferred embodiment of the present invention, the described etherifying agent of step (1) is trifluoroethanol sodium and trifluoroethanol, N, dinethylformamide, 1, a kind of mixture in 3-dimethyl-2-imidazolone, the tetramethylene sulfone.
As a preferred embodiment of the present invention, the described etherifying agent of step (1) is trifluoroethanol potassium and trifluoroethanol, N, dinethylformamide, 1, a kind of mixture in 3-dimethyl-2-imidazolone, the tetramethylene sulfone.
As a preferred embodiment of the present invention, the described etherifying agent of step (1) is trifluoroethanol lithium and trifluoroethanol, N, dinethylformamide, 1, a kind of mixture in 3-dimethyl-2-imidazolone, the tetramethylene sulfone.
As one embodiment of the invention, step (1) temperature of reaction is-10～100 ℃, preferred 25～50 ℃.
As one embodiment of the invention, the described reductive agent of step (2) is a hydrogen, and the used catalyzer of hydrogenating reduction is a palladium carbon, platinum carbon or Raney's nickel; Used solvent is the alcohol of C1～C4, toluene, 1,4-dioxane or N, dinethylformamide.
As a preferred embodiment of the present invention, in the hydrogenation reduction 3, the mass ratio of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) oil of mirbane and catalyzer is 1: (0.05～1), preferred 1: (0.1～0.3); Temperature of reaction is 0～100 ℃, preferred 25～45 ℃.
As one embodiment of the invention, the described reductive agent of step (2) is an iron powder, and use ammonium chloride as ionogen, 3,5-two fluoro-4-(2,2,2-trifluoro ethoxy) mol ratio of oil of mirbane and iron powder, ammonium chloride is 1: (0.5～5): (0.1～1), preferred 1: (2.5～4): (0.2～0.4); Temperature of reaction is 50～120 ℃, preferred 80～100 ℃.
As a preferred embodiment of the present invention, the acid of using in the step (3) is Hydrogen bromide, sulfuric acid or hydrochloric acid, preferred Hydrogen bromide; The diazotization reaction temperature is-20～20 ℃, preferred-10～0 ℃.
As a preferred embodiment of the present invention, step steams product by the distillatory method when reaction is carried out in (3).
As a preferred embodiment of the present invention, the consumption of cuprous bromide is in the step (3): 3, and the mol ratio of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) aniline and cuprous bromide is 1: (0.1～2), preferred 1: (0.4～0.8); The temperature of reaction of diazotization reaction product and cuprous bromide is 50～150 ℃, preferred 80～130 ℃.
Description of drawings
Fig. 1 is 3 of embodiment 1 provided by the present invention, the hydrogen spectrum spectrogram of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) oil of mirbane.
Fig. 2 is 3 of embodiment 7 provided by the present invention, the hydrogen spectrum spectrogram of 4-two fluoro-5-trifluoro ethoxy aniline.
Fig. 3 is 3 of embodiment 12 provided by the present invention, the hydrogen spectrum spectrogram of 4-two fluoro-5-trifluoro ethoxy bromobenzenes.
Embodiment
Following type reaction is used for illustrating the present invention.Within the technical scheme that those skilled in that art all belong to the present invention to the simple replacement done of invention or improvement etc. and protected.
Embodiment 1:3, the preparation of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) oil of mirbane
Drop into trifluoroethanol 210g (2.1mol) in the 500ml four-hole bottle, be cooled to 20 ℃ under stirring, slowly add 95% potassium hydroxide 42g (0.713mol), the adition process heat release is obvious, and attention can not disposablely be poured into, add in batches.Finish and be warmed up to 60 ℃ and be stirred to potassium hydroxide and all dissolve, cool to 35 ℃, standby.
Drop into 3,4 in another 1000ml four-hole bottle, 5-trifluoronitrobenzene 124g (0.7mol) finishes, and is cooled to 25 ℃, the trifluoroethanol solution of the potassium hydroxide that in 25～30 ℃ of droppings, goes on foot, and the heat release of dropping process is obvious, notes controlled temperature.About 1.5～2h dropwises, and finishes slowly to be warmed up to 40 ℃ insulation 3h.Finish the back underpressure distillation and reclaim trifluoroethanol, recyclable trifluoroethanol 160g.Then the still temperature is cooled to 85 ℃, adds tap water 250ml, keep 65～70 ℃ of still temperature, stir 30min, leave standstill 30min, layering.Can get oil reservoir 176g, content 99.3%, yield 97.8%.
3, the hydrogen of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) oil of mirbane is composed spectrogram as shown in Figure 1, data analysis:
1H-NMR (CDCl
3, 500Hz) δ: 4.62 (m, 2H), 7.92 (m, 2H).
Embodiment 2:3, the preparation of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) oil of mirbane
Press embodiment 1, with the sodium hydroxide replacement potassium hydroxide solution of 30g 95% (0.713mol), reaction obtains oil reservoir 169g, content 99.0%, yield 93.9%.
Embodiment 3:3, the preparation of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) oil of mirbane
Press embodiment 1, the amount of trifluoroethanol reduces to 140g (1.4mol), and reaction obtains oil reservoir 140g, content 97.9%, yield 77.8%.
Embodiment 4:3, the preparation of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) oil of mirbane
Press embodiment 1, temperature of reaction is brought up to 55 ℃, and reaction obtains oil reservoir 160g, content 95.2%, yield 88.9%.
Embodiment 5:3, the preparation of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) oil of mirbane
Drop into trifluoroethanol 400g in the 1000ml four-hole bottle, slowly add trifluoroethanol potassium 95.9g (0.7mol) under stirring, the adition process heat release is obvious, and attention can not disposablely be poured into, add in batches.Finishing heats up is stirred to trifluoroethanol potassium and all dissolves, and cooling is standby again.
Drop into 3,4 in another 2000ml four-hole bottle, 5-trifluoronitrobenzene 124g (0.7mol) finishes, and is cooled to 25 ℃ under stirring, the trifluoroethanol solution of step trifluoroethanol potassium in 25～30 ℃ of droppings, and the heat release of dropping process is obvious, notes controlled temperature.About 1.5～2h dropwises.Finish and slowly be warmed up to 40 ℃, insulation 3h.Heat up, trifluoroethanol is reclaimed in air distillation, reclaims trifluoroethanol 360g.Then the still temperature is cooled to 85 ℃, adds tap water 250ml, keep 65～70 ℃ of still temperature, stir 30min, leave standstill 30min, layering.Can get the oil reservoir 170.9g of lower floor, content 99.5%, yield 95.0%.
Embodiment 6:3, the preparation of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) oil of mirbane
Press embodiment 5, with 400g N, dinethylformamide replaces trifluoroethanol, and reaction obtains oil reservoir 167.5g, content 99.0%, yield 93.1%.
Embodiment 7:3, the preparation of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) aniline
In the 500ml autoclave, drop into previous step oil reservoir 100g, ethanol 200ml, 5%Pd/C 15g is 10kg/cm3 at hydrogen pressure, reaction 6h when temperature of reaction is 35～40 ℃, reaction solution is poured out and filtered, and filtrate decompression concentrates and obtains 3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) aniline 86.1g, content 99.0%, yield 97.5%.
3, the hydrogen of 4-two fluoro-5-trifluoro ethoxy aniline is composed spectrogram as shown in Figure 2, data analysis:
1H-NMR (CDCl
3, 500Hz) δ: 3.73 (s, 2H), 4.31 (m, 2H), 6.22 (m, 2H).
Embodiment 8:3, the preparation of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) aniline
Press embodiment 7, replace 5%Pd/C with the 15g Raney's nickel, reaction obtains product 83.6g, content 98.2%, yield 94.6%.
Embodiment 9:3, the preparation of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) aniline
Press embodiment 7, reaction 6h obtains product 85.4g, content 85.6%, yield 96.7% when temperature is 60 ℃.
Embodiment 10:3, the preparation of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) aniline
In the 500ml four-hole bottle, drop into water 150g, ammonium chloride 7.4g (0.12mol), iron powder 65.4g (1.167mol), be warming up to 95 ℃, insulation 30min drips previous step oil reservoir 100g (0.389mol), finish insulation 2.5h, cooling will be poured out the stillness of night, in bottle, add 300g methyl alcohol, stir after-filtration, collect filtrate, add 100g water after removing solvent under reduced pressure, separatory obtains organic layer 77.8g, content 98.9%, yield 88.1%.
Embodiment 11:3, the preparation of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) aniline
Press embodiment 10, the amount of iron powder reduces to 43.6g (0.778mol), and reaction obtains product 67.9g, content 97.8%, yield 76.9%.
Embodiment 12:3, the preparation of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) bromobenzene
Drop into water 30ml in the 500ml four-hole bottle, Glacial acetic acid 30g, on go on foot reduzate 25g (0.11mol), be warmed up to 60 ℃ under stirring, insulation 20min slowly drips 40% hydrobromic acid solution 80g then, 60～80 ℃ of control still temperature, 1h finishes, elder generation's water cooling is to room temperature, and the cryosel cooling is-8 ℃ again, adds trash ice 30g, slowly drip the solution that 9g Sodium Nitrite and 18g water are made into then, control reaction temperature is-5～0 ℃.Finish, stirred 5 minutes, eliminate excessive nitrous acid, get diazonium liquid with thionamic acid 0.5g.
In another 500ml four-hole bottle, drop into CuBr12.3g (0.055mol), add 40% Hydrogen bromide 13g then, be heated to boiling after, the limit drips diazonium liquid limit product is distilled, and steams until no oil droplet, stops to distill, and can get oil-water mixture, gets oil reservoir.Can go up column distillation after merging many batches, can obtain 3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) bromobenzene 28g, content 99.8%, yield 87.5% according to conversion after the many batches of distillations.
3, the hydrogen of 4-two fluoro-5-trifluoro ethoxy bromobenzenes is composed spectrogram as shown in Figure 3, data analysis:
1H-NMR (CDCl
3, 500Hz) δ: 4.43 (m, 2H), 7.11 (s, 1H), 7.13 (s, 1H).
Embodiment 13:3, the preparation of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) bromobenzene
Press embodiment 12, replace the Hydrogen bromide of 80g 40% with the sulfuric acid of 48g 40%, reaction obtains 3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) bromobenzene 23.5g, content 99.5%, yield 73.4%.
Embodiment 14:3, the preparation of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) bromobenzene
Press embodiment 12, the diazotization reaction temperature is brought up to 0～5 ℃, and reaction obtains reaction and obtains 3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) bromobenzene 18.6g, content 99.0%, yield 58.1%.
Embodiment 15:3, the preparation of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) bromobenzene
Press embodiment 12, the amount of cuprous bromide reduces to 6.34g (0.044mol), reaction to 3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) bromobenzene 20g, content 98%, yield 62.5%.
Claims (10)
1. one kind 3, the preparation method of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) bromobenzene is characterized in that, realizes by following reaction:
Concrete steps are:
(1) 3,4,5-trifluoronitrobenzene and etherifying agent react, and generate 3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) oil of mirbane;
The reduction reaction takes place and generates 3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) aniline in (2) 3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) oil of mirbane under the effect of reductive agent;
(3) 3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) aniline carries out diazotization reaction under the effect of diazo reagent, the diazotization reaction product generates 3,5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) bromobenzene with the cuprous bromide reaction again.
Wherein the etherifying agent that uses in the step (1) is the trifluoroethanol solution of alkali, perhaps etherifying agent is a kind of and trifluoroethanol, the N in trifluoroethanol potassium, trifluoroethanol sodium or the trifluoroethanol lithium, dinethylformamide, 1, a kind of mixture in 3-dimethyl-2-imidazolone or the tetramethylene sulfone;
Reductive agent in the step (2) is hydrogen or iron powder;
Diazo reagent in the step (3) is Sodium Nitrite and sour mixed solution.
2. method according to claim 1 is characterized in that the used etherifying agent of step (1) is the trifluoroethanol solution of alkali, and described alkali is potassium hydroxide, sodium hydroxide, calcium hydroxide or lithium hydroxide, preferred potassium hydroxide; And 3,4, the mol ratio of 5-trifluoronitrobenzene and trifluoroethanol, alkali is 1: (1～5): (0.1～2), preferred 1: (2.5～3.5): (0.8～1.5); Temperature of reaction is-10～100 ℃, preferred 25～50 ℃.
3. method according to claim 1, it is characterized in that the used etherifying agent of step (1) is a kind of and trifluoroethanol, the N in trifluoroethanol potassium, trifluoroethanol sodium or the trifluoroethanol lithium, dinethylformamide, 1, a kind of mixture in 3-dimethyl-2-imidazolone or the tetramethylene sulfone, and 3,4, the mol ratio of 5-trifluoronitrobenzene and trifluoroethanol potassium, trifluoroethanol sodium or trifluoroethanol lithium is 1: (0.5～2), preferred 1: (0.8～1.5); 3,4,5-trifluoronitrobenzene and trifluoroethanol, N, dinethylformamide, 1, a kind of mass ratio in 3-dimethyl-2-imidazolone or the tetramethylene sulfone is 1: (1～5), preferred 1: (3～4).
4. according to the described method of claim 1,2 or 3, it is characterized in that the temperature of reaction of step (1) is-10～100 ℃, preferred 25～50 ℃.
5. method according to claim 1 is characterized in that the used reductive agent of step (2) is a hydrogen, and the hydrogenating reduction catalyst system therefor is palladium carbon, platinum carbon or Raney's nickel; Used solvent is C
1～C
4Alcohol, toluene, 1,4-dioxane or N, dinethylformamide.
6. method according to claim 5 is characterized in that in the step (2) 3, and the mass ratio of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) oil of mirbane and catalyzer is 1: (0.05～1), preferred 1: (0.1～0.3); Temperature of reaction is 0～100 ℃, preferred 25～45 ℃.
7. method according to claim 1, it is characterized in that the used reductive agent of step (2) is an iron powder, and use ammonium chloride as ionogen, 3,5-two fluoro-4-(2,2,2-trifluoro ethoxy) mol ratio of oil of mirbane and iron powder, ammonium chloride is 1: (0.5～5): (0.1～1), preferred 1: (2.5～4): (0.2～0.4); Temperature of reaction is 50～120 ℃, preferred 80～100 ℃.
8. method according to claim 1 is characterized in that in the step (3), described acid is Hydrogen bromide, sulfuric acid or hydrochloric acid, preferred Hydrogen bromide; The diazotization reaction temperature is-20～20 ℃, preferred-10～0 ℃.
9. method according to claim 1 is characterized in that by the distillatory method product being steamed when reaction is carried out in the step (3).
10. method according to claim 1 is characterized in that the consumption of cuprous bromide in the step (3) is: 3, and the mol ratio of 5-two fluoro-4-(2,2, the 2-trifluoro ethoxy) aniline and cuprous bromide is 1: (0.1～2), preferred 1: (0.4～0.8); The temperature of reaction of diazotization reaction product and cuprous bromide is 50～150 ℃, preferred 80～130 ℃.
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| CN103664511A (en) * | 2013-12-13 | 2014-03-26 | 上虞市临江化工有限公司 | Preparation method of 5-bromo-1,3-dichloro-2-fluorobenzene |
| CN104086376A (en) * | 2014-07-21 | 2014-10-08 | 西安近代化学研究所 | Liquid crystal midbody containing difluoro methyl ether bridged bond and synthesis method thereof |
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| JP4164054B2 (en) * | 2003-10-10 | 2008-10-08 | 松下電器産業株式会社 | Semiconductor device having polysilicon fuse |
| CN101497566A (en) * | 2009-03-10 | 2009-08-05 | 太仓制药厂 | Preparation of 2,5-bis(2,2,2-trifluoro ethoxy) benzene carbonic acid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103664511A (en) * | 2013-12-13 | 2014-03-26 | 上虞市临江化工有限公司 | Preparation method of 5-bromo-1,3-dichloro-2-fluorobenzene |
| CN103664511B (en) * | 2013-12-13 | 2015-07-08 | 浙江林江化工股份有限公司 | Preparation method of 5-bromo-1,3-dichloro-2-fluorobenzene |
| CN104086376A (en) * | 2014-07-21 | 2014-10-08 | 西安近代化学研究所 | Liquid crystal midbody containing difluoro methyl ether bridged bond and synthesis method thereof |
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