CN103396318A - Synthetic process for 2,4-dinitroanisole - Google Patents
Synthetic process for 2,4-dinitroanisole Download PDFInfo
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- CN103396318A CN103396318A CN2013103258398A CN201310325839A CN103396318A CN 103396318 A CN103396318 A CN 103396318A CN 2013103258398 A CN2013103258398 A CN 2013103258398A CN 201310325839 A CN201310325839 A CN 201310325839A CN 103396318 A CN103396318 A CN 103396318A
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- dinitroanisol
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- 238000000034 method Methods 0.000 title claims abstract description 35
- CVYZVNVPQRKDLW-UHFFFAOYSA-N 2,4-dinitroanisole Chemical compound COC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O CVYZVNVPQRKDLW-UHFFFAOYSA-N 0.000 title abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 195
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000003513 alkali Substances 0.000 claims abstract description 35
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000012065 filter cake Substances 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 118
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 45
- LOTKRQAVGJMPNV-UHFFFAOYSA-N 1-fluoro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C([N+]([O-])=O)=C1 LOTKRQAVGJMPNV-UHFFFAOYSA-N 0.000 claims description 37
- 239000000706 filtrate Substances 0.000 claims description 27
- 239000012452 mother liquor Substances 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 239000006210 lotion Substances 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 13
- 239000000395 magnesium oxide Substances 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- 229960001708 magnesium carbonate Drugs 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 43
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 230000008025 crystallization Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 150000007529 inorganic bases Chemical class 0.000 abstract 1
- 238000001514 detection method Methods 0.000 description 24
- 238000003756 stirring Methods 0.000 description 13
- 238000009413 insulation Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 235000021463 dry cake Nutrition 0.000 description 4
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
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Abstract
The invention discloses a synthetic process for 2,4-dinitroanisole. The synthetic process comprises the following steps of: heating and dissolving composite inorganic base into methanol to obtain a methanol alkali solution, then dropwise adding the methanol alkali solution into a methanol solution containing the 2,4-dinitroanisole to react, after finishing the reaction, carrying out cooling crystallization on the obtained reaction liquid, filtering to obtain a filter cake and filter liquid, washing the filter cake by utilizing water of 30-35 DEG C to obtain solids and washing liquid, and drying the obtained solids to obtain 2,4-dinitroanisole; and regulating the pH of the obtained washing liquid to be 2-4, and carrying out the cooling crystallization, filtering, water washing and drying to obtain 2,4-dinitrophenol. The synthetic process has the advantages that the purity and yield of the 2,4-dinitroanisole are improved, the water volume of mother liquid is effectively reduced, and the mother liquid can be continuously and mechanically applied after being processed, is accordant with industrial production requirements and can be used for industrial production.
Description
Technical field
The invention belongs to the catalyst preparation technical field, be specifically related to a kind of 2, the synthesis technique of 4-dinitroanisol.
Background technology
2,4-dinitroanisol (CAS:119-27-7) is a kind of important fine-chemical intermediate, can be used for the field of fine chemical such as dyestuff, medicine and agricultural chemicals.Traditional 2, the 4-dinitroanisol is mainly to make solvent with methyl alcohol, with mineral alkali, do acid binding agent and 2, the 4-DNCB reaction makes, wherein, methyl alcohol is raw material, is again reaction solvent, from cost, catalytic efficiency and availability, consider, the mineral alkali of using in reaction is generally the aqueous solution of sodium hydroxide.In the technique of having reported at present, generally need a large amount of methyl alcohol make solvent, and use the aqueous solution of sodium hydroxide to make in reaction and bring large water gaging into, long reaction time, after reaction, mother liquor can not continue recycled, produces a large amount of waste water, and environmental hazard is large; Because of the strong basicity of liquid caustic soda, the DNFB hydrolysis generates 2 simultaneously, the amount of 2, 4-dinitrophenol increases, general gained 2,4-dinitroanisol and 2, the 2, 4-dinitrophenol total recovery is no more than 95%, and for synthetic 2, the report of 4-dinitroanisol purity seldom.
Along with increasingly sharpening and national increasingly stringent to environmental improvement of market competition, recently for producing 2 of a large amount of waste water, 4-dinitroanisol liquid caustic soda method synthesis technique is also being updated, mainly be centered around and how reduce methanol usage, simplification synthesis technique, as CN1146450A, CN102391126A; Also be reported in the liquid caustic soda reaction system and add phase-transfer catalyst, but Reaction time shorten improves the transformation efficiency of DNFB to a certain extent, but all do not related to the report of mother liquid recycle.
Publication number is that the Chinese patent application of CN1146450A discloses a kind of employing 2, the 4-dinitrochlorobenzene prepares 2, the method of 4-dinitroanisol, this reaction is reacted as acid binding agent with 40% aqueous sodium hydroxide solution, temperature of reaction is 50～55 ℃, the reaction obtain 2, the yield of 4-dinitroanisol is 95%, but the content of 2,4-DNP contained in product is not described further.
Publication number is that the Chinese patent application of CN102391126A discloses a kind of employing 2, the 4-dinitrochlorobenzene prepares 2 as raw material, 4-dinitroanisol and 2, the method of 2, 4-dinitrophenol, the method are usingd 10%～40% sodium hydroxide solution and are reacted as acid binding agent, and temperature of reaction is 56～70 ℃, obtain 2, the mixture of 4-dinitroanisol and 2,4-DNP, then obtain respectively product separately through separating.
In the processing method of having reported, in reaction, constantly drip liquid caustic soda, due to the strong basicity of liquid caustic soda, at a certain temperature, accelerated the DNFB hydrolysis, the content of byproduct 2,4-DNP increases, make 2,4-dinitroanisol purity drop, yield also reduces; Simultaneously adding of liquid caustic soda, the reaction water yield increases, and after reaction, produces a large amount of waste water, and mother liquor can not continue recycled, then produces a large amount of waste water, and environment is produced to larger harm, simultaneously the also corresponding increase of cost of aftertreatment technology.
Summary of the invention
The invention provides a kind of 2, the synthesis technique of 4-dinitroanisol, this synthesis technique can obtain 2,4-dinitroanisol with highly selective and high yield, reduces the generation of 2,4-DNP.
A kind of 2, the synthesis technique of 4-dinitroanisol, comprise the steps:
The heating of composite inorganic alkali is dissolved in methyl alcohol and obtains methyl alcohol alkali lye, then drip described methyl alcohol alkali lye to containing 2, in the methanol solution of 4-dinitrochlorobenzene, react, after reaction completes, by the reaction solution decrease temperature crystalline that obtains, then filter and obtain filter cake and filtrate, the gained filter cake obtains solid and washing lotion with 30～35 ℃ of water washings, resulting solid obtains described 2 through super-dry, the 4-dinitroanisol;
Resulting washing lotion is adjusted pH to 2～4, through crystallisation by cooling, filtration, washing and drying, obtains 2,4-DNP;
Described composite inorganic alkali is comprised of the alkali of sodium hydroxide and calcic or magnesium.
In the present invention, the alkali of described calcic or magnesium is pH value conditioning agent, after compound with sodium hydroxide, can effectively suppress the hydrolysis of DNFB, reduces the generation of 2,4-DNP, improves yield and the purity of 2,4-dinitroanisol.Simultaneously, the alkali of sodium hydroxide and calcic or magnesium carries out compound in methanol solvate, has reduced the use of a large amount of aqueous solution, has reduced the discharging of waste water.
As preferably, the alkali of described calcic or magnesium is at least a in magnesium oxide, calcium oxide, magnesiumcarbonate, calcium carbonate, after these four kinds of alkali and sodium hydroxide are compound, can suppress better the hydrolysis of DNFB.
As further preferred, the mol ratio of the alkali of described sodium hydroxide and described calcic or magnesium is 15～25:1.The consumption of sodium hydroxide is too high, can make in product the byproduct 2,4-DNP must measure increase; The consumption of sodium hydroxide is too low, and the transformation efficiency of DNFB is reduced, and can affect equally yield and the purity of 2,4-dinitroanisol.
As preferably, 2, the mol ratio of the methyl alcohol in the methyl alcohol in 4-dinitrochlorobenzene, described methanol solution, composite inorganic alkali and described methyl alcohol alkali lye is 1:2～4:1.02～1.08:3～5, by the consumption that increases methyl alcohol, can suitably improve described 2, the purity of 4-dinitroanisol, but the consumption of methyl alcohol is difficult for too much, otherwise can make product 2, the 4-dinitroanisol is dissolved in methyl alcohol, reduces product 2, the yield of 4-dinitroanisol.
The raising of temperature of reaction can increase the transformation efficiency of reaction, but excess Temperature can be accelerated the hydrolysis of described DNFB, can make on the contrary described 2, the yield of 4-dinitroanisol and purity drop, as preferably, the temperature of reaction is 70～75 ℃.
Described methyl alcohol alkali lye adds in reaction solution by the mode that drips, and rate of addition is unsuitable too fast, otherwise can cause local concentration of lye too high, and temperature rises too fast, and side reaction increases, and as preferably, the time for adding of described methyl alcohol alkali lye is 30～45 minutes.
The reaction degree of carrying out can be monitored by HPLC or TLC, and as preferably, the reaction times is 3～6 hours.
Last handling process after reaction finishes is as follows: reaction solution is directly lowered the temperature, under stirring, be cooled to room temperature, suction filtration after crystallization, obtain filter cake and filtrate, filter cake obtains solid and washing lotion with the neutrality that is washed to of 30～35 ℃, obtain 2, the 4-dinitroanisol, purity (HPLC) is more than 99%, and yield is more than 95%.The gained washing lotion is regulated crystallisation by cooling under ℃ stirring of pH=2～4,5～15 with 31% technical hydrochloric acid, filters, and is washed to neutrality, obtains the byproduct 2,4-DNP, and purity (HPLC) is more than 98%, and yield is no more than 3%.
As preferably, described filtrate obtains mother liquor and distillate after underpressure distillation;
The mother liquid obtained recycled that carries out;
The gained distillate reclaims methyl alcohol through rectifying, and this methyl alcohol can be used as solvent and again participates in reaction, and the purpose of rectifying is for further purification methyl alcohol, removes the water that produces in reaction, guarantees that recycling afterreaction system is anhydrous.
Compared with the existing technology, beneficial effect of the present invention is embodied in: the aqueous solution that replaces sodium hydroxide in reaction with the methyl alcohol alkali lye of inorganic compounding alkali, not only improve reaction preference, reduced the generation of by product 2,4-DNP, and effectively reduced methanol usage, mother liquor is sustainable applying mechanically after treatment, and wastewater flow rate reduces, and has reduced environmental pollution, greatly reduce simultaneously waste water aftertreatment cost, can carry out suitability for industrialized production.
The accompanying drawing explanation
Fig. 1 is of the present invention 2, the schema of the synthesis technique of 4-dinitroanisol.
Embodiment
Flow process below in conjunction with specific embodiment and Fig. 1 is described in further detail the present invention.
Embodiment 1
(1) in the four-hole boiling flask of 150mL, add methyl alcohol 32g(1mol), under stirring, slowly add solid sodium hydroxide 16g(0.4mol) and magnesium oxide 0.8g(0.02mol), control temperature and be no more than 65 ℃ to the complete molten methyl alcohol alkali lye that obtains of solid, stand-by.
(2) in the four-hole boiling flask of 500mL, add methyl alcohol 45g(1.41mol), under stirring, add DNFB 81g(0.4mol), be heated to DNFB entirely molten.Drip the methyl alcohol alkali lye that complete step (1) obtains in 30min, 70 ℃ of insulation reaction 3 hours.After be cooled to room temperature, suction filtration after crystal is separated out, collect filtrate 83g, filtrate after underpressure distillation mother liquor 45g.Filter cake, with the neutrality that is washed to of 30 ℃, is collected washing lotion, and dry cake obtains 2,4-dinitroanisol 76.4g, and in DNFB, yield is 96.3%, liquid chromatographic detection purity 99.3%.The gained washing lotion is regulated pH=2～4 with 31% hydrochloric acid, stirs lower 5～15 ℃ of crystallisation by cooling, filters, and is washed to neutrality, obtains 2,4-DNP 1.66g, in DNFB, and yield 2.25%, liquid chromatographic detection purity 98.5%.
Mother liquid recycle: (3) add methyl alcohol 32g(1mol in the four-hole boiling flask of 150mL), under stirring, slowly add solid sodium hydroxide 16g(0.4mol) and magnesium oxide 0.8g(0.02mol), control temperature be no more than 65 ℃ entirely molten, stand-by to solid.
(4) in the four-hole boiling flask of 500mL, add mother liquor 45g, methyl alcohol 27g(0.85mol) add DNFB 81g(0.4mol under stirring), be heated to DNFB entirely molten.Drip the methyl alcohol alkali lye that complete step (3) obtains in 30min, 70 ℃ of insulation reaction 3 hours.After cool to room temperature, suction filtration after crystal is separated out, collect filtrate 80g, gained filtrate obtained to mother liquor 45.3g after underpressure distillation, filter cake is with the neutrality that is washed to of 30 ℃, collect washing lotion, dry cake obtains 2,4-dinitroanisol 76.9g, with 2,4-dinitrochlorobenzene meter, yield are 97.0%, liquid chromatographic detection purity 99.0%.The gained washing lotion is regulated pH=2～4 with 31% hydrochloric acid, stirs lower 5～15 ℃ of crystallisation by cooling, filters, and is washed to filter cake neutrality, obtains 2,4-DNP 1.67g, in DNFB, and yield 2.27%, liquid chromatographic detection purity 98.2%.After mother liquid recycle, the total productive rate of the product that obtains slightly has rising, and purity does not descend substantially.
Embodiment 2
By in the described method of embodiment 1, in step (1), adding methyl alcohol 40g(1.25mol).
In step (2), add methyl alcohol 50g(1.56mol), 72 ℃ of insulation reaction 5 hours.Obtain filtrate 96g, the mother liquor 58g of filtrate after underpressure distillation, 2,4-dinitroanisol 76.0g, in DNFB, yield is 95.8%, liquid chromatographic detection purity 99.8%.Obtain 2,4-DNP 1.77g, in DNFB, yield 2.4%, liquid chromatographic detection purity 99.0%.
Mother liquid recycle: by adding methyl alcohol 40g(1.25mol in the described method of embodiment 1 in step (3)).
In step (4), add mother liquor 58g, methyl alcohol 25.6g(0.8mol), 72 ℃ of insulation reaction 5 hours.Obtain filtrate 108g, 2,4-dinitroanisol 76.5g, in DNFB, yield is 96.5%, liquid chromatographic detection purity 99.5%.By after the distillation of 108g filtrate decompression, obtaining mother liquor 58g, obtain 2,4-DNP 1.80g, in DNFB, yield 2.44%, liquid chromatographic detection purity 98.7%.
Embodiment 3
By in the described method of embodiment 1, in step (1), adding methyl alcohol 44.8g(1.4mol).
In step (2), add methyl alcohol 57.6g(1.8mol), 75 ℃ of insulation reaction 6 hours.Obtain filtrate 110g, the mother liquor 70g of filtrate after underpressure distillation, obtain 2,4-dinitroanisol 75.3g, and in DNFB, yield is 95%, liquid chromatographic detection purity 99.5%.Obtain 2,4-DNP 2.12g, in DNFB, yield 2.88%, liquid chromatographic detection purity 98.3%.
Mother liquid recycle: by adding methyl alcohol 44.8g(1.4mol in the described method of embodiment 1 in step (3)).
In step (4), add mother liquor 70g, methyl alcohol 28.8g(1.8mol), 75 ℃ of insulation reaction 6 hours.Obtain filtrate 105g, the mother liquor 70g of filtrate after underpressure distillation, obtain 2,4-dinitroanisol 75.5g, and in DNFB, yield is 95.2%, liquid chromatographic detection purity 99.3%.Obtain 2,4-DNP 2.15g, in DNFB, yield 2.92%, liquid chromatographic detection purity 98.2%.
Embodiment 4
By in the described method of embodiment 1, in step (1), adding methyl alcohol 40g(1.25mol), solid sodium hydroxide 16.6g(0.415mol) and magnesium oxide 0.72g(0.018mol).
In step (2), add methyl alcohol 51.2g(1.6mol), 72 ℃ of insulation reaction 5 hours.Obtain filtrate 98g, the mother liquor 57g of filtrate after underpressure distillation, obtain 2,4-dinitroanisol 75.7g, and in DNFB, yield is 95.5%, liquid chromatographic detection purity 99.6%.Obtain 2,4-DNP 1.78g, in DNFB, yield 2.42%, liquid chromatographic detection purity 98.8%.
Mother liquid recycle: by adding methyl alcohol 40g(1.25mol in the described method of embodiment 1 in step (3)) solid sodium hydroxide 16.6g(0.415mol) and magnesium oxide 0.72g(0.018mol).
In step (4), add mother liquor 57g, methyl alcohol 16g(0.5mol), 72 ℃ of insulation reaction 5 hours.Obtain filtrate 88g, filtrate obtains mother liquor 57.2g, 2 after underpressure distillation, 4-dinitroanisol 76g, in DNFB, yield is 95.8%, liquid chromatographic detection purity 99.2%, 2,4-DNP 1.84g, with 2,4-dinitrochlorobenzene meter, yield 2.50%, liquid chromatographic detection purity 98.5%.
Embodiment 5
By in the described method of embodiment 1, in step (1), adding methyl alcohol 40g(1.25mol), solid sodium hydroxide 15.6g(0.39mol) and magnesium oxide 0.72g(0.018mol).
In step (2), add methyl alcohol 51.2g(1.6mol), 72 ℃ of insulation reaction 5 hours.Obtain filtrate 99g, filtrate obtains mother liquor 58.3g after underpressure distillation, 2,4-dinitroanisol 75.3g, and in DNFB, yield is 95.0%, liquid chromatographic detection purity 99.2%.2,4-DNP 1.62g, in DNFB, yield 2.2%, liquid chromatographic detection purity 98.6%.
Mother liquid recycle:
By in the described method of embodiment 1, in step (3), adding methyl alcohol 40g(1.25mol) solid sodium hydroxide 15.6g(0.415mol) and magnesium oxide 0.72g(0.018mol).
In step (4), add mother liquor 58.3g, methyl alcohol 12.8g(0.4mol), 72 ℃ of insulation reaction 5 hours.Obtain filtrate 104g, the mother liquor 58.2g of filtrate after underpressure distillation, obtain 2,4-dinitroanisol 75.4g, and in DNFB, yield is 95.1%, liquid chromatographic detection purity 99%.2,4-DNP 1.64g, in DNFB, yield 2.23%, liquid chromatographic detection purity 98.5%.
With calcium oxide or the calcium carbonate of equivalent, replace magnesium oxide can obtain identical catalytic effect.
Comparative Examples 1
In the four-hole boiling flask of 500mL, add methyl alcohol 48g(1.5mol), under stirring, add DNFB 81g(0.4mol), be heated to DNFB entirely molten.Drip 10% aqueous sodium hydroxide solution 168g, wherein sodium hydrate content is 16.4g(0.41mol), in 30min, drip and finish.70 ℃ of insulation reaction 3 hours.After be cooled to room temperature, adjust behind pH to 8～10 crystallization under room temperature, suction filtration after crystal is separated out, filter cake is with the neutrality that is washed to of 30 ℃, collect washing lotion, dry cake obtains 2,4-dinitroanisol 39.3g, with 2,4-dinitrochlorobenzene meter, yield are 49.6%, liquid chromatographic detection purity 96.2%.The gained washing lotion is regulated pH=2～4 with 31% hydrochloric acid, stirs lower 5～15 ℃ of crystallisation by cooling, filters, and is washed to neutrality, obtains 2,4-DNP 35.5g, in DNFB, and yield 48.2%, liquid chromatographic detection purity 95.6%.
Comparative Examples 2
(1) in the four-hole boiling flask of 150mL, add methyl alcohol 32g(1mol), under stirring, slowly add solid sodium hydroxide 16.8g(0.42mol), control temperature and be no more than 65 ℃ to the complete molten methyl alcohol alkali lye that obtains of solid, stand-by.
(2) in the four-hole boiling flask of 500mL, add methyl alcohol 45g(1.41mol), under stirring, add DNFB 81g(0.4mol), be heated to DNFB entirely molten.Drip the methyl alcohol alkali lye that complete step (1) obtains in 30min, 70 ℃ of insulation reaction 3 hours.After be cooled to room temperature, suction filtration after crystal is separated out, collect filtrate 81g, filtrate after underpressure distillation mother liquor 45g.Filter cake, with the neutrality that is washed to of 30 ℃, is collected washing lotion, and dry cake obtains 2,4-dinitroanisol 75.2g, and in DNFB, yield is 94.8%, liquid chromatographic detection purity 98.5%.The gained washing lotion is regulated pH=2～4 with 31% hydrochloric acid, stirs lower 5～15 ℃ of crystallisation by cooling, filters, and is washed to neutrality, obtains 2,4-DNP 2.5g, in DNFB, and yield 3.39%, liquid chromatographic detection purity 97.2%.
Claims (8)
1. one kind 2, the synthesis technique of 4-dinitroanisol, it is characterized in that, comprise the steps: the heating of composite inorganic alkali is dissolved in methyl alcohol and obtains methyl alcohol alkali lye, then drip described methyl alcohol alkali lye to containing 2, in the methanol solution of 4-dinitrochlorobenzene, react, after reaction completes, by the reaction solution decrease temperature crystalline that obtains, then filter and obtain filter cake and filtrate, the gained filter cake obtains solid and washing lotion with 30～35 ℃ of water washings, and it is described 2 that resulting solid drying obtains, the 4-dinitroanisol;
Resulting washing lotion is adjusted pH to 2～4, through crystallisation by cooling, filtration, washing and drying, obtains 2,4-DNP;
Described composite inorganic alkali is comprised of the alkali of sodium hydroxide and calcic or magnesium.
2. according to claim 12, the synthesis technique of 4-dinitroanisol, is characterized in that, the alkali of described calcic or magnesium is at least a in magnesium oxide, calcium oxide, magnesiumcarbonate, calcium carbonate.
3. according to claim 1 and 22, the synthesis technique of 4-dinitroanisol, is characterized in that, the mol ratio of the alkali of described sodium hydroxide and described calcic or magnesium is 15～25:1.
4. according to claim 1 and 22, the synthesis technique of 4-dinitroanisol, it is characterized in that, the mol ratio of the methyl alcohol in the methyl alcohol in DNFB, described methanol solution, composite inorganic alkali and described methyl alcohol alkali lye is 1:2～4:1.02～1.08:3～5.
5. according to claim 1 and 22, the synthesis technique of 4-dinitroanisol, is characterized in that, the temperature of reaction is 70～75 ℃.
6. according to claim 1 and 22, the synthesis technique of 4-dinitroanisol, is characterized in that, the time of reaction is 3～6 hours.
7. according to claim 1 and 22, the synthesis technique of 4-dinitroanisol, is characterized in that, the time for adding of described methyl alcohol alkali lye is 30～45 minutes.
8. according to claim 12, the synthesis technique of 4-dinitroanisol, is characterized in that, described filtrate obtains mother liquor and distillate after underpressure distillation;
Resulting mother liquor carries out recycled;
Resulting distillate reclaims methyl alcohol through rectifying.
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| CN105777550A (en) * | 2016-05-13 | 2016-07-20 | 湖北东方化工有限公司 | Method for continuously synthesizing 2,4-dimitroanisole |
| CN111187168A (en) * | 2019-12-12 | 2020-05-22 | 中卫市鑫三元化工有限公司 | Clean production process for producing nitrobenzene alkoxy ether by using nitrohalogenated benzene |
| CN114163353A (en) * | 2021-12-14 | 2022-03-11 | 郑州大学 | Preparation method of anisyl nitrile |
| CN114507141A (en) * | 2021-12-23 | 2022-05-17 | 中北大学 | A kind of method for controlling 2,4-dinitroanisole crystal form |
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| CN105566121A (en) * | 2014-10-11 | 2016-05-11 | 中国石油化工股份有限公司 | Method for reducing generation of nitrophenol in preparation process of nitroanisole |
| CN105777550A (en) * | 2016-05-13 | 2016-07-20 | 湖北东方化工有限公司 | Method for continuously synthesizing 2,4-dimitroanisole |
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| CN111187168A (en) * | 2019-12-12 | 2020-05-22 | 中卫市鑫三元化工有限公司 | Clean production process for producing nitrobenzene alkoxy ether by using nitrohalogenated benzene |
| CN114163353A (en) * | 2021-12-14 | 2022-03-11 | 郑州大学 | Preparation method of anisyl nitrile |
| CN114163353B (en) * | 2021-12-14 | 2024-05-28 | 郑州大学 | Preparation method of anisic nitrile |
| CN114507141A (en) * | 2021-12-23 | 2022-05-17 | 中北大学 | A kind of method for controlling 2,4-dinitroanisole crystal form |
| CN114507141B (en) * | 2021-12-23 | 2024-01-23 | 中北大学 | Method for controlling 2,4-dinitroanisole crystal form |
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