CN105859560B - The method for improving the nitration reaction nitro product yield of the benzyl chloride of biphenyl two - Google Patents
The method for improving the nitration reaction nitro product yield of the benzyl chloride of biphenyl two Download PDFInfo
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- CN105859560B CN105859560B CN201610311080.1A CN201610311080A CN105859560B CN 105859560 B CN105859560 B CN 105859560B CN 201610311080 A CN201610311080 A CN 201610311080A CN 105859560 B CN105859560 B CN 105859560B
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Abstract
The invention discloses the method for the nitration reaction nitro product yield for improving the benzyl chloride of biphenyl two, under acetyl nitrate nitrification system, β zeolites are selected as catalyst, 8 16h are reacted at 10 30 DEG C of reaction temperature, after adding water stopped reaction, after extracting target solution with dichloromethane, successively to organic phase solution saturated sodium carbonate solution, distillation water washing, with the 30h of anhydrous sodium sulfate drying 24, solvent is rotated with Rotary Evaporators and produces nitro product.The effective of the present invention is：Nitro product yield can repeatedly recycle up to 89.0% and catalyst.
Description
Technical field
The invention mainly relates to the benzyl chloride of biphenyl two nitrification is improved, the nitration reaction nitro production of the benzyl chloride of biphenyl two is specifically improved
The method of thing yield.
Background technology
Nitro product purposes after many known benzyl chloride nitration reactions of biphenyl two is quite varied, at present the nitre of the benzyl chloride of biphenyl two
Change reaction and mainly use nitric acid-sulfuric acid system, nitric acid-sulfuric acid system is industrially to nitrify widely used system, still
Due to nitric acid-sulfuric acid system, not only selectivity of product is poor, and spent acid, contaminated wastewater environment caused by reaction.
The content of the invention
To solve deficiency of the prior art, the present invention provides a kind of nitration reaction nitro product for improving the benzyl chloride of biphenyl two
The method of yield, increases the yield of the nitro product after biphenyl two benzyl chloride nitration reaction, and reduces spent acid, waste water in reaction
Discharge, catalyst can be recycled repeatedly in addition, be economized on resources.
The present invention to achieve the above object, is achieved through the following technical solutions：
The method for improving the nitration reaction nitro product yield of the benzyl chloride of biphenyl two, is comprised the following steps that：
(1) benzyl chloride of 0.1-1g biphenyl two is firstly added into container, then acetic anhydride is added into container, to the benzyl chloride of biphenyl two
It is completely dissolved to obtain initial soln；
(2) 0.01-0.8g beta-zeolite is added into initial soln；
(3) nitric acid that mass fraction is 90-95% is added dropwise into initial soln, makes nitric acid with initial soln at 10-30 DEG C
Lower reaction 8-16h, obtains reaction solution；
(4) 10-20ml water, stopped reaction are added into reaction solution；
(5) liquid in container is filtered, obtains filter residue and filtrate, the filtrate is target solution；
(6) target solution is extracted with dichloromethane first, obtains organic phase solution and aqueous phase solution and carry out liquid separation, extracted
After 3-5 times, merge organic phase solution, then organic phase solution is washed 1-3 times with saturated sodium carbonate solution, then washed with distillation
Wash, until stopping washing when organic phase solution is neutral, 24-30h finally is dried to organic phase solution with anhydrous sodium sulfate；
(7) above-mentioned dried organic phase solution is filtered into obtain filtrate, filtrate is transferred to totally dry round-bottomed flask
In, solvent is rotated with Rotary Evaporators and produces nitro product.
After the filter residue reclaimed to step (5) is dried, it is calcined at 500~600 DEG C to white, kept dry, and
Reused 2-4 times in step (2).
When extracting target solution with dichloromethane in step (6), the usage amount of dichloromethane is reduced successively.
Initial soln is stirred on side in step (3), and the nitric acid that mass fraction is 90-95% is added dropwise in side.
When step (4) adds 10-20ml water stopped reactions into reaction solution, stirring reaction solution 25-40min.
When extracting target solution with dichloromethane in step (6), target solution 25-40min is stirred after adding dichloromethane.
Contrast and prior art, beneficial effect of the present invention are：
1st, the present invention can increase the yield of the nitro product after the benzyl chloride nitration reaction of biphenyl two, and reduce in reaction and give up
Acid, the discharge of waste water.
2nd, the present invention uses beta-zeolite repeatedly to recycle, economize on resources as catalyst.
3rd, when the present invention extracts target solution with dichloromethane, the usage amount of dichloromethane is reduced successively, reduces dichloromethane
The usage amount of alkane, economize on resources, environmental protection.
4th, stirring initial soln in side of the present invention, side are added dropwise nitric acid, are advantageous to initial soln and are fully contacted with nitric acid, accelerate anti-
Speed is answered, and reaction can be cooled, is reacted at 10 DEG C -30 DEG C, can suitably be accelerated reaction speed, also can
Prevent temperature is too high from can decompose nitric acid.0.1-0.2mL nitric acid is slowly added dropwise into container, the addition of nitric acid is very few, bottom
The conversion ratio of thing is low, and the addition of nitric acid is excessive, easily causes the generation of accessory substance.
5th, when the present invention adds 10-20ml water stopped reactions into reaction solution, stirring reaction solution 25-40min, accelerate
The cessation speed of reaction, prevent reaction from continuing to produce more accessory substance, reduce nitro product yield.
6th, when the present invention extracts target solution with dichloromethane, 25- is stirred after adding dichloromethane to target solution
40min, dichloromethane is fully contacted with target solution, make the organic phase solution in target solution be easier to be extracted by dichloromethane
Take out.
Brief description of the drawings
Accompanying drawing 1 is the gas phase analysis chromatogram of embodiment 2；
Accompanying drawing 2 is 2- nitros -4,4 in embodiment 2 '-dichloromethyl biphenyl1H NMR scheme.
Embodiment
With reference to the drawings and specific embodiments, the invention will be further described.It should be understood that these embodiments are merely to illustrate
The present invention rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, this area
Technical staff can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims
Limited range.
Example 1：The benzyl chloride nitrification of biphenyl two prepares the experiment of nitro product：
The accurate benzyl chloride of 4-4 biphenyl two for weighing 0.3g is placed in 50ml round-bottomed flasks, and adding 10ml acetic anhydrides makes 4-4 biphenyl
Two benzyl chlorides are completely dissolved to obtain initial soln, add 0.2g β -40 (one kind of beta-zeolite) and are used as catalyst, then experimental assembly is put
In the nitric acid that 0.1ml mass fractions are 90% in constant temperature blender with magnetic force, is slowly added dropwise while stirring, reacted, reaction side
Formula is：
Reaction solution is obtained after 8h is reacted at 25 DEG C, 10mL water is added into reaction solution makes reaction whole in round-bottomed flask
Only, continue to stir 30min or so, add 15mL dichloromethane extractive reaction solution, 25min is stirred, by round-bottomed flask
Reaction solution filtered, carry out recovery filter residue, filtrate is fully transferred to stratification in separatory funnel, and lower floor is organic phase
Solution, upper strata are aqueous phase solution, lower floor's liquid are put into totally dry small beaker by funnel lower end, upper strata aqueous phase adds
A small amount of dichloromethane extraction, merges organic phase solution after extracting 3 times, is washed 1 time with 10mL saturated sodium carbonate solutions, then use 10mL
Washing 3 times, detection organic phase solution for after neutral by organic phase solution be placed in it is clean dry in small beaker, add appropriate anhydrous
Sodium sulphate dries 24h, and organic phase solution is filtered, and filtrate is transferred in totally dry round-bottomed flask will with Rotary Evaporators
Solvent is rotated, and obtained solid is weighed, and is therefrom weighed 0.06g and is completely dissolved with 1ml dichloromethane, is surveyed with gas chromatograph
Determine constituent content, the conversion ratio of nitrobiphenyl reaches 97.3%-99.8%, 2- nitro -4, and the yield of the benzyl chloride of 4 '-biphenyl two reaches
86.5-89.0%.
Example 2：
The gas chromatographic analysis that the nitro product obtained using the benzyl chloride nitration reaction of biphenyl two as described in Example 1 is carried out is real
Test.Experimental result as shown in Figure 1 and Figure 2, wherein,1H NMR(600MHz,CDCl3) δ 7.91 (s, 1H), 7.65 (d, J=9.3Hz,
1H), 7.44 (dd, J=12.6,8.0Hz, 3H), 7.30 (d, J=8.1Hz, 2H), 4.66 (s, 2H), 4.63 (s, 2H).
Example 3：
The accurate benzyl chloride of 4-4 biphenyl two for weighing 0.5g is placed in 100ml round-bottomed flasks, and adding 15ml acetic anhydrides joins 4-4
The benzyl chloride of benzene two is completely dissolved to obtain initial soln, adds 0.5g β -150 (one kind of beta-zeolite) and is used as catalyst, then by experimental assembly
It is placed in constant temperature blender with magnetic force, the nitric acid that 0.2ml mass fractions are 93% is slowly added dropwise while stirring, is reacted, reacts
Equation is：
After 15 DEG C of reaction 16h, after reaction solution, into reaction solution add 15mL water makes reaction whole in round-bottomed flask
Only, continue to stir 30min or so, add 15mL dichloromethane extractive reaction solution, 25min is stirred, by round-bottomed flask
Reaction solution filtered, carry out recovery filter residue, filtrate is fully transferred to stratification in separatory funnel, and lower floor is organic phase
Solution, upper strata are aqueous phase solution, lower floor's liquid are put into totally dry small beaker by funnel lower end, upper strata aqueous phase adds
A small amount of dichloromethane extraction, merges organic phase solution after extracting 3 times, is washed 1 time with 10mL saturated sodium carbonate solutions, then use 10mL
Washing 3 times, detection organic phase solution for after neutral by organic phase solution be placed in it is clean dry in small beaker, add appropriate anhydrous
Sodium sulphate dries 28h, and organic phase solution is filtered, and filtrate is transferred in totally dry round-bottomed flask will with Rotary Evaporators
Solvent is rotated, and obtained solid is weighed, and is therefrom weighed 0.06g and is completely dissolved with 1ml dichloromethane, is surveyed with gas chromatograph
Determine constituent content, the conversion ratio of nitrobiphenyl reaches 89.4%-99.8%, 2- nitro -4, and the yield of the benzyl chloride of 4 '-biphenyl two reaches
85.3-89.0%.
Example 4：
The accurate benzyl chloride of 4-4 biphenyl two for weighing 0.8g is placed in 100ml round-bottomed flasks, and adding 18ml acetic anhydrides joins 4-4
The benzyl chloride of benzene two is completely dissolved to obtain initial soln, adds 0.7g β -280 (one kind of beta-zeolite) and is used as catalyst, then by experimental assembly
It is placed in constant temperature blender with magnetic force, the nitric acid that 0.25ml mass fractions are 95% is slowly added dropwise while stirring, is reacted, reacts
Equation is：
Reaction solution is obtained after 15 DEG C of reaction 10h, 20mL water is added into reaction solution makes reaction terminating in round-bottomed flask,
Continue to stir 30min or so, add 15mL dichloromethane extractive reaction solution, stir 25min, will be anti-in round-bottomed flask
Answer solution to be filtered, carry out recovery filter residue, filtrate is fully transferred to stratification in separatory funnel, and lower floor mixes to be organic
Liquid, upper strata are aqueous phase solution, lower floor's liquid are put into totally dry small beaker by funnel lower end, upper strata aqueous phase adds few
Dichloromethane extraction is measured, merges organic phase solution after extracting 3 times, is washed 1 time with 10mL saturated sodium carbonate solutions, then with 10mL's
Washing 3 times, detection organic phase solution are totally dried in small beaker to be placed in organic phase solution after neutrality, add appropriate anhydrous sulphur
Sour sodium dries 30h, and organic phase solution is filtered, and filtrate is transferred to will be molten with Rotary Evaporators in totally dry round-bottomed flask
Agent is rotated, and obtained solid is weighed, and is therefrom weighed 0.06g and is completely dissolved with 1ml dichloromethane, uses gas chromatograph for determination
Constituent content, the conversion ratio of nitrobiphenyl reach 89.4%-99.8%, 2- nitro -4, and the yield of the benzyl chloride of 4 '-biphenyl two reaches
86.3-89.0%.
Embodiment 5：
Filter residue is reclaimed, after filter residue is calcined into 8h at 550 DEG C, it is beta-zeolite that filter residue, which is changed into white, kept dry, is continued
For being catalyzed the benzyl chloride nitration reaction of 4-4 biphenyl two.Experiment condition reclaims catalyst, 0.5g 4-4 biphenyl accurately to weigh 0.5g
Two benzyl chlorides, the nitric acid that acetic anhydride 15ml, 0.1ml mass fraction are 95%, react 16h at 25 DEG C.15mL water is added to burn in round bottom
Make reaction terminating in bottle, continue to stir 40min, add 15mL dichloromethane stirring 30min.By the reaction in round-bottomed flask
Solution is filtered, and carries out recovery filter residue again, and filtrate is fully transferred to stratification in separatory funnel, by lower floor's liquid by leaking
Bucket lower end is put into totally dry small beaker, and upper strata aqueous phase adds a small amount of dichloromethane extraction, merges organic phase, uses 10mL
Saturated sodium carbonate solution washs 1 time, then the washing 3 times with 10mL, by organic phase be placed in it is clean dry in small beaker, add appropriate
Anhydrous sodium sulfate drying 24h, filtrate is transferred in totally dry round-bottomed flask after filtering and revolved solvent with Rotary Evaporators
Evaporate, obtained solid is weighed, therefrom weigh 0.06g and be completely dissolved with 1ml dichloromethane, with gas chromatograph for determination component
Content, the conversion ratio of nitrobiphenyl reach 99.1%-99.6%, 2- nitro -4, and the yield of the benzyl chloride of 4 '-biphenyl two reaches
84.3.1-85.6%.Recycled again after the catalyst use regenerated after recovery, catalyst has reclaimed three times, altogether
Obtain higher nitro product yield.
Claims (4)
1. improve the method for the nitration reaction nitro product yield of the benzyl chloride of biphenyl two, it is characterised in that：Comprise the following steps that：
(1) benzyl chloride of 0.1-1g biphenyl two is firstly added into container, then acetic anhydride is added into container, it is complete to the benzyl chloride of biphenyl two
Dissolving obtains initial soln；
(2) 0.01-0.8g beta-zeolite is added into initial soln；
(3) side stirring initial soln, while the nitric acid that 0.05-0.25mL mass fractions are 90-95% is added dropwise into initial soln, make
Nitric acid reacts 8-16h with initial soln at 10-30 DEG C, obtains reaction solution；
(4) 10-20ml water is added into reaction solution, stopped reaction, continues stirring reaction solution 25-40min after stopped reaction；
(5) liquid in container is filtered, obtains filter residue and filtrate, reclaim filter residue, the filtrate is target solution；
(6) target solution is extracted with dichloromethane first, organic phase solution and aqueous phase solution is obtained, by organic phase solution and aqueous phase
Solution carries out liquid separation, after extracting 3-5 times, merges organic phase solution；Then organic phase solution is washed with saturated sodium carbonate solution
1-3 times；Again with distillation water washing, stop washing when organic phase solution is neutral；Finally with anhydrous sodium sulfate to organic phase
24-30h is dried in solution；
(7) above-mentioned dried organic phase solution is filtered into obtain filtrate, filtrate be transferred in totally dry round-bottomed flask, used
Solvent rotation is evaporated and produces nitro product by Rotary Evaporators.
2. the method for the nitration reaction nitro product yield according to claim 1 for improving the benzyl chloride of biphenyl two, its feature exist
In：After the filter residue reclaimed to step (5) is dried, it is calcined at 500~600 DEG C to white, kept dry, and in step
(2) reused 2-4 times in.
3. the method for the nitration reaction nitro product yield according to claim 1 for improving the benzyl chloride of biphenyl two, its feature exist
In：When extracting target solution with dichloromethane in step (6), the usage amount of dichloromethane is reduced successively.
4. the method for the nitration reaction nitro product yield according to claim 1 for improving the benzyl chloride of biphenyl two, its feature exist
In：When extracting target solution with dichloromethane in step (6), target solution 25-40min is stirred after adding dichloromethane.
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