CN105481654A - Tubular continuous o-fluorophenol production method - Google Patents
Tubular continuous o-fluorophenol production method Download PDFInfo
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- CN105481654A CN105481654A CN201510856044.9A CN201510856044A CN105481654A CN 105481654 A CN105481654 A CN 105481654A CN 201510856044 A CN201510856044 A CN 201510856044A CN 105481654 A CN105481654 A CN 105481654A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/045—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/20—Diazonium compounds
Abstract
The present invention discloses a tubular continuous o-fluorophenol production method comprising tubular diazo reaction of a nitrosyl sulfuric acid solution and an o-fluoroaniline solution in a tubular reactor to obtain a diazo solution; tubular hydrolysis reaction of the diazo solution and a copper sulphate water solution in the tubular reactor to obtain a hydrolysis solution; and after-treatment of the hydrolysis solution to obtain o-fluorophenol. The method uses the tubular reactor for the tubular diazo reaction and the tubular hydrolysis reaction to solve the phenomenon of material backmixing and uneven temperature distribution of kettle-type reaction, reduces the incidence of side effects, and improves the yield of the product.
Description
Technical field
The invention belongs to organic intermediate synthesis field, be specifically related to the method that pipe type continuously produces adjacent fluorophenol.
Background technology
Adjacent fluorophenol is mainly used in the fluorine-containing antibacterial-anti-inflammatory drug of synthesizing new and sterilant, kills the intermediate of cerate, weedicide and liquid crystal material.
The synthetic method preparing adjacent fluorophenol is a lot, divides the phenol low temperature fluorate method that mainly contains, o-fluorobenzyl bromide hydrolysis method, adjacent fluoroaniline diazotization hydrolysis method etc. by raw material route.
1, be dissolved in appropriate solvent by phenol, make it be cooled to-10 ~-3 DEG C, then pass into the fluorine gas with nitrogen dilution, make it react, obtain adjacent fluorophenol and p-fluorophenol, the ratio of the two is 57:14, the square formula 1 of synthesis equation:
Equation 1
This operational path not only will use dangerous very high fluorine gas, and adjacent fluorophenol and p-fluorophenol two kinds of isomer in product are more difficult is separated, and also has tarry by product and generates.
2, take o-fluorobenzyl bromide as raw material, join in autoclave by itself and hydrated barta, water, copper and a small amount of catalyzer, at high temperature reaction for some time obtains adjacent fluorophenol, square formula 2.
Equation 2
This method yield is better, but o-fluorobenzyl bromide price is almost identical with adjacent fluorophenol, and the method is almost without economic benefit.
3, with adjacent fluoroaniline for raw material, use Sodium Nitrite diazotization, then in diluted acid, pyrohydrolysis obtains adjacent fluorophenol.The advantage of this method is that operation is succinct, reaction conditions is gentle, raw material sources are convenient, and shortcoming to generate containing sodium salt spent acid, must regularly process.
Summary of the invention
The invention provides a kind of method that pipe type continuously produces adjacent fluorophenol, the method adopts the pipe type continuously mode of production, solves the problems such as material back mixing that still reaction exists and temperature of charge skewness.
Pipe type continuously produces a method for adjacent fluorophenol, comprises the following steps:
Step (1): nitrosyl-sulfuric acid solution and adjacent fluoroaniline solution are carried out tubular type doazo reaction in tubular reactor, obtains diazo liquid; Wherein, the molar feed ratio of adjacent fluoroaniline and nitrosyl-sulfuric acid is 1:1.1 ~ 1:1.3; The temperature of tubular type doazo reaction is 0 ~ 30 DEG C;
Step (2): diazo liquid and copper sulfate solution carry out tubular type hydrolysis reaction at tubular reactor, obtain hydrolyzed solution; The concentration of copper sulfate solution is 10% ~ 30wt%, and hydrolysis liquid temperature is 105 ~ 135 DEG C;
Step (3): hydrolyzed solution obtains adjacent fluorophenol through aftertreatment.
The square formula 3 of synthetic route of the present invention:
Equation 3
Present method carries out tubular type doazo reaction and tubular type hydrolysis reaction in tubular reactor, solves material back mixing and the temperature of charge phenomenon pockety of still reaction existence, decreases the generation of side reaction (as azo product).Meanwhile, the present invention also adopts nitrosyl-sulfuric acid as nitroso-group donor, effectively improves the product yield of tubular type doazo reaction; And avoid the sodium salt problem using Sodium Nitrite to introduce, the recycle of copper sulfate and unclassified stores (as sulfuric acid) can be realized, reduce wastewater and waste acid to the pollution of environment.
In step (1), containing nitrosyl-sulfuric acid in nitrosyl-sulfuric acid solution, other are sulfuric acid, phosphoric acid or other mineral acids.
As preferably, described nitrosyl-sulfuric acid solution is the mixing solutions of nitrosyl-sulfuric acid and sulfuric acid, and wherein, the concentration of nitrosyl-sulfuric acid is 25% ~ 45wt%.
Under this nitrosyl-sulfuric acid concentration, the product yield of pipe reaction is high, and reaction controllability is good.
In step (1), adjacent fluoroaniline dissolves and obtains described adjacent fluoroaniline solution in organic solvent, and the molar feed ratio of adjacent fluoroaniline and organic solvent is 1:2 ~ 4; Described organic solvent be preferably water-insoluble low boiling point solvent, further preferably, described organic solvent be methylene dichloride, ethyl acetate, tetrahydrofuran (THF) (THF), methyl tertiary butyl ether (MTBE) one or more.
The nitrosyl-sulfuric acid solution of described concentration is mixed through static mixer respectively by volume pump with adjacent fluoroaniline solution, with each reaction raw materials active ingredient, the molar feed ratio of adjacent fluoroaniline and nitrosyl-sulfuric acid is 1:1.1 ~ 1.3, enters in tubular reactor and carry out tubular type doazo reaction after mixing of materials.The transformation efficiency of adjacent fluoroaniline in tubular reactor is high, and two phase reaction can effectively be avoided diazonium salt and adjacent fluoroaniline to react generating diazoamino compound, the content of reduction by product.Two phase reaction effectively can be avoided diazonium salt and adjacent fluoroaniline to react and generate diazoamino compound.
Obtained diazo liquid is transferred in diazonium container for storing liquid (being equivalent to surge tank).In order to enhance productivity and reduce storage risk, the diazo liquid in diazonium container for storing liquid should be transferred in the tubular reactor of tubular type hydrolysis reaction as early as possible, generates stable adjacent fluorophenol.
In step (2), copper sulfate solution enters tubular reactor by volume pump with diazo liquid after static mixer mixes, and the diazonium vitriol in diazo liquid is hydrolyzed under the catalysis of copper sulfate, and obtained hydrolyzed solution enters in hydrolysis container for storing liquid.Under the concentration and temperature of described copper sulfate, the hydrolysis effect of diazo liquid is good, and by product is less.Further preferably, the concentration of copper sulfate solution is 20% ~ 25%, and hydrolysis liquid temperature is 120 ~ 130 DEG C.
In step (2), the molar ratio of diazonium vitriol and copper sulfate is 1:1-2.
Hydrolyzed solution is refined through aftertreatment and is obtained object product (adjacent fluorophenol), and described aftertreatment comprises the following steps:
Step (3): hydrolyzed solution extracts to obtain extraction liquid and raffinate acid solution through extraction agent;
Step (4): extraction liquid carries out rectification process, collects adjacent fluorophenol cut, and the extraction agent that other cuts are used as step (3) recycles;
Raffinate acid solution low temperature crystallization recovery copper sulfate;
Raffinate acid solution concentrates, low temperature crystallization recovery copper sulfate; Mix with nitric acid after residue acid solution concentrates again, and be used as absorption liquid sulfur dioxide absorption, the nitrosyl-sulfuric acid solution A obtained is as the nitrosyl-sulfuric acid solution recovery of step (1).
Extraction agent described in step (3) is hydrophobic organic solvent.
As preferably, described extraction agent is one or more of methylene dichloride, toluene, dimethylbenzene, ether, propyl ether, ethyl acetate, propyl acetate, butylacetate, acetone, espeleton and mibk.
In actual mechanical process, leave standstill to complete layering after hydrolysis reaction terminates, organic phase is for subsequent use, and the described extraction agent of water layer extracts, and extract layer and organic phase merge and be namely extracted liquid.Extraction liquid to boil product containing adjacent fluorophenol, extraction agent and a small amount of height, through rectification process, collect object product frac, remaining cut contains the material such as described extraction agent, a small amount of object product, can direct cycle in step (3) and reuse as extraction agent.
Raffinate acid solution (the lower floor of extraction, i.e. aqueous phase) containing the material such as copper sulfate, sulfuric acid, through concentrated, crystallisation by cooling reclaim(ed) sulfuric acid copper, the copper sulfate water preparation of recovery, to the copper sulfate solution of concentration required for the present invention, is circulated to step (1) and reuses.As preferably, the temperature of raffinate acid solution low temperature crystallization is-15 ~ 10 DEG C.
The residue acid solution of crystallization reclaim(ed) sulfuric acid copper continues concentrated, adds nitric acid, then passes into sulfurous gas, prepare nitrosyl-sulfuric acid solution A, after the nitrosyl-sulfuric acid concentration of nitrosyl-sulfuric acid solution A reaches 25% ~ 45wt%, be circulated to step (1), participate in tubular type doazo reaction.Effectively can be reduced the production cost of object product by this processing mode, reduce the processing load of spent acid waste water.
In order to improve the preparation efficiency of nitrosyl-sulfuric acid solution A, further reduction production cost, in Industrial processes, nitrosyl-sulfuric acid solution A reacts obtained with the mixed solution (absorption liquid) of residue acid solution and nitric acid by sulfurous gas in the film-falling absorption tower of plural serial stage.As, the mixed solution of residue acid solution and nitric acid is entered by the second film-falling absorption tower entrance, and through the second falling film absorption tower counter-flow to the first film-falling absorption tower, sulfurous gas air-flow is contrary with absorption liquid liquid flow path direction.Absorb saturated after by first film-falling absorption tower export extraction, obtain nitrosyl-sulfuric acid solution A.As preferably, in the mixed solution of residue acid solution and nitric acid, the content of nitric acid is not less than 20wt%.
In the present invention, tubular reactor is adopted to carry out tubular type doazo reaction and tubular type hydrolysis reaction, solve material back mixing and the temperature of charge phenomenon pockety of still reaction existence, decrease the generation of side reaction, improve the yield of product, achieve continuous prodution simultaneously, improve production efficiency; Coordinate the use of nitrosyl-sulfuric acid simultaneously, increase the stability of diazonium vitriol, improve doazo reaction yield; And there is not sodium salt enrichment phenomenon, the recycle of sulfuric acid and copper sulfate can be realized.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet that pipe type continuously provided by the invention produces the method for adjacent fluorophenol.
Embodiment
Embodiment 1
Step (1): tubular type doazo reaction: pump into the adjacent fluoroaniline of 220Kg and 600Kg methylene dichloride in stirring tank, after stirring in the adjacent fluoroaniline header tank of suction; Then pump in stirring tank
660Kg nitrosyl-sulfuric acid solution (nitrosyl-sulfuric acid concentration is 45.8wt%) and the 355Kg vitriol oil, after stirring in suction nitrosyl-sulfuric acid header tank.Open two header tank bottom valve doors, control flow proportional is 1:1.24, enters tubular type doazo reaction device by static mixer after being mixed, the molar ratio 1:1.2 of adjacent fluoroaniline and nitrosyl-sulfuric acid; Temperature controls at 20 DEG C, and the diazo liquid of generation enters in container for storing liquid.
Step (2): tubular type hydrolysis reaction: drop into 550Kg cupric sulfate pentahydrate and 1210Kg water in reactor, stirs in the rear suction copper-bath header tank of clarification; By in the diazo liquid suction diazo liquid header tank in diazo liquid container for storing liquid.Open two header tank bottom valve doors, control flow proportional is 1:1.43, enters pipe type water solution reactor by static mixer after being mixed, and temperature controls at 130 DEG C, and the hydrolyzed solution of generation enters in hydrolyzed solution container for storing liquid.
Step (3): aftertreatment: drop into 1000Kg methylene dichloride (extraction agent) in hydrolyzed solution, the oil reservoir separated (extraction liquid) is transferred to rectifying workshop and carries out rectifying, and rectifying tower is collected the low methylene dichloride boiled and recycled; Middle colourless transparent liquid component is adjacent fluorophenol, obtains colourless transparent liquid 192Kg altogether, purity 99.91%, yield 86.43%.Other cuts that rectifying is collected are circulated to step (3) and reuse as extraction agent.Water layer (raffinate acid solution) is refrigerated separation after dewatering and concentrating, and obtains copper sulfate crystal 520Kg, the rate of recovery 94.55%; Residue acid solution mixes with concentrated nitric acid after again concentrating, and sulfur dioxide absorption obtains nitrosyl-sulfuric acid solution A, is back to step (1) and participates in tubular type doazo reaction.
Embodiment 2
Step (1): add nitric acid in the residue acid solution that embodiment 1 reclaims, the massfraction being uniformly mixed nitric acid in the mixed solution obtained is 25.5wt%.Sulfur dioxide absorption in the film-falling absorption tower of two-stage tandem, when the nitrosyl-sulfuric acid concentration in the nitrosyl-sulfuric acid solution A obtained is 30wt%, extraction nitrosyl-sulfuric acid solution A.
Step (2): tubular type doazo reaction: the dichloromethane solution adding adjacent fluoroaniline (220Kg) in stirring tank, in the adjacent fluoroaniline-methylene dichloride header tank of the suction that stirs; Then in stirring tank, the nitrosyl-sulfuric acid solution A 1000kg that step (1) is obtained is pumped into, after stirring in suction nitrosyl-sulfuric acid header tank.Open two header tank bottom valve doors, the molar ratio controlling adjacent fluoroaniline and nitrosyl-sulfuric acid is 1:1.2.Enter tubular type doazo reaction device after static mixer mixes, temperature controls at 20 DEG C, and the diazo liquid of generation enters in container for storing liquid.
Step (3): tubular type hydrolysis reaction: the copper sulfate that embodiment 1 is reclaimed and water stirring and dissolving in suction copper-bath (20wt%) header tank; By in the diazo liquid suction diazo liquid header tank in diazo liquid container for storing liquid.Open two header tank bottom valve doors, enter pipe type water solution reactor by static mixer after being mixed, temperature controls at 130 DEG C, and the hydrolyzed solution of generation enters in hydrolyzed solution container for storing liquid.
Step (4): extraction: hydrolyzed solution layering, organic phase is for subsequent use, and the cut extraction that aqueous phase reclaims by embodiment 1, merges (extraction liquid) by organic phase, and is transferred to rectifying workshop and carries out rectifying, and low cut recycling of boiling collected by rectifying tower; Middle colourless transparent liquid component is adjacent fluorophenol, obtains colourless transparent liquid 190Kg altogether, purity 99.90%, yield 84.63%.
Water layer (raffinate acid solution) is refrigerated separation after dewatering and concentrating, and obtains copper sulfate crystal 498Kg, the rate of recovery 90.55%; Residue acid solution prepares the recycle of nitrosyl-sulfuric acid solution A.
Embodiment 3
Step (1): tubular type doazo reaction: by adjacent for 44.4g fluoroaniline and 240g methylene dichloride mixing and stirring (adjacent fluoroaniline solution); 132g nitrosyl-sulfuric acid (46.16wt%) and 66g vitriol oil mixing and stirring (nitrosyl-sulfuric acid solution).Pumped in silicone tube together with nitrosyl-sulfuric acid solution by adjacent fluoroaniline solution respectively by peristaltic pump and carry out diazotization reaction, silicone tube is placed in 20 DEG C of water-baths, and intraductal retention time is 15s.
Step (2): tubular type hydrolysis reaction: 100g cupric sulfate pentahydrate and 200g water are mixedly configured into clear liquor and mix with diazo liquid (maintaining liquid temperature 20 DEG C).Pumped in silicone tube by peristaltic pump and carry out tubular type hydrolysis reaction, pipe range 20m, silicone tube is placed in 135 DEG C of oil baths, and intraductal retention time is 20min, obtains hydrolyzed solution.
Step (3): extraction: separate organic layer after hydrolyzed solution layering; Use methylene dichloride (2 × 150ml) aqueous layer extracted, add after extraction in organic layer and divide to fall moisture, remove on the rotary evaporator and reclaim methylene dichloride, obtaining adjacent fluorophenol crude product 41.81g, purity 91.24%, two-step reaction molar yield is 85.15%.
Hydrolyzed solution process: solids removed by filtration tar, is cooled to-10 DEG C of standing crystallizatioies, direct suction filtration to cupric sulfate pentahydrate crystal 94g, the rate of recovery 94%.
Embodiment 4
Step (1): tubular type doazo reaction: by adjacent for 44.4g fluoroaniline and 240g methylene dichloride mixing and stirring (adjacent fluoroaniline solution); Adjacent fluoroaniline solution and 190g nitrosyl-sulfuric acid solution (mass percent of nitrosyl-sulfuric acid is 35.0%) are carried out diazotization reaction by pumping in silicone tube together with peristaltic pump, wherein, the molar ratio of adjacent fluoroaniline and nitrosyl-sulfuric acid is 1:1.3, silicone tube is placed in 20 DEG C of water-baths, and intraductal retention time is 15s.
Step (2): tubular type hydrolysis reaction: 100g cupric sulfate pentahydrate and 200g water are mixedly configured into clear liquor and mix with diazo liquid (maintaining liquid temperature 20 DEG C).Pumped in silicone tube by peristaltic pump and carry out tubular type hydrolysis reaction, pipe range 20m, silicone tube is placed in 105 DEG C of oil baths, and intraductal retention time is 20min, obtains hydrolyzed solution.
Step (3): extraction: separate organic layer after hydrolyzed solution layering; Use methylene dichloride (2 × 150ml) aqueous layer extracted, add after extraction in organic layer and divide to fall moisture, remove on the rotary evaporator and reclaim methylene dichloride, obtaining adjacent fluorophenol crude product 42.05g, purity 88.73%, two-step reaction molar yield is 83.28%.
Embodiment 5
Step (1): tubular type doazo reaction: by adjacent for 44.4g fluoroaniline and 150gEA mixing and stirring (adjacent fluoroaniline solution); Adjacent fluoroaniline solution and 204g nitrosyl-sulfuric acid solution (mass percent of nitrosyl-sulfuric acid is 30.0%) are carried out diazotization reaction by pumping in silicone tube together with peristaltic pump, wherein, the molar ratio of adjacent fluoroaniline and nitrosyl-sulfuric acid is 1:1.2, silicone tube is placed in 0 DEG C of water-bath, and intraductal retention time is 15s.
Step (2): tubular type hydrolysis reaction: 100g cupric sulfate pentahydrate and 200g water are mixedly configured into clear liquor and mix with diazo liquid (maintaining liquid temperature 20 DEG C).Pumped in silicone tube by peristaltic pump and carry out tubular type hydrolysis reaction, pipe range 20m, silicone tube is placed in 125 DEG C of oil baths, and intraductal retention time is 20min, obtains hydrolyzed solution.
Step (3): extraction: separate organic layer after hydrolyzed solution layering; Use EA (2 × 150ml) aqueous layer extracted, add after extraction in organic layer and divide to fall moisture, remove on the rotary evaporator and reclaim ethyl acetate, obtain adjacent fluorophenol crude product 41.5g, purity 90.24%, two-step reaction molar yield is 83.59%.
Comparative example 1
Compare with embodiment 3, difference is, changes tubular reactor into common tank reactor.After reaction terminates, obtain adjacent fluorophenol crude product 40.29g, purity 87.10%, two-step reaction molar yield is 78.53%.
Comparative example 2
Compare with embodiment 3, difference is, adopts the Sodium Nitrite of equimolar amount to substitute nitrosyl-sulfuric acid and participates in tubular type doazo reaction.After reaction terminates, obtain adjacent fluorophenol crude product 36.56g, purity 81.20%, two-step reaction molar yield is 71.30%.
Claims (8)
1. pipe type continuously produces a method for adjacent fluorophenol, it is characterized in that, comprises the following steps:
Step (1): nitrosyl-sulfuric acid solution and adjacent fluoroaniline solution are carried out tubular type doazo reaction in tubular reactor, obtains diazo liquid; Wherein, the molar feed ratio of adjacent fluoroaniline and nitrosyl-sulfuric acid is 1:1.1 ~ 1.3; The temperature of tubular type doazo reaction is 0 ~ 30 DEG C;
Step (2): diazo liquid and copper sulfate solution carry out tubular type hydrolysis reaction in tubular reactor, obtain hydrolyzed solution; The concentration of copper sulfate solution is 10% ~ 30wt%, and the temperature of tubular type hydrolysis reaction is 105 ~ 135 DEG C;
Step (3): hydrolyzed solution obtains adjacent fluorophenol through aftertreatment.
2. pipe type continuously as claimed in claim 1 produces the method for adjacent fluorophenol, and it is characterized in that, described nitrosyl-sulfuric acid solution is the mixing solutions of nitrosyl-sulfuric acid and sulfuric acid, and wherein, the concentration of nitrosyl-sulfuric acid is 25% ~ 45wt%.
3. pipe type continuously as claimed in claim 2 produces the method for adjacent fluorophenol, it is characterized in that, adjacent fluoroaniline dissolves and obtains described adjacent fluoroaniline solution in organic solvent, and the molar feed ratio of adjacent fluoroaniline and organic solvent is 1:2 ~ 4; Described organic solvent be methylene dichloride, ethyl acetate, tetrahydrofuran (THF), methyl tertiary butyl ether one or more.
4. the pipe type continuously as described in any one of claim 1-3 produces the method for adjacent fluorophenol, it is characterized in that, described aftertreatment comprises the following steps:
Step (3): hydrolyzed solution extracts to obtain extraction liquid and raffinate acid solution through extraction agent;
Step (4): extraction liquid carries out rectification process, collects adjacent fluorophenol cut, and the extraction agent that other cuts are used as step (3) recycles;
Raffinate acid solution concentrates, low temperature crystallization recovery copper sulfate; Mix with nitric acid after residue acid solution concentrates again, and be used as absorption liquid sulfur dioxide absorption, the nitrosyl-sulfuric acid solution A obtained is as the nitrosyl-sulfuric acid solution recovery of step (1).
5. pipe type continuously as claimed in claim 4 produces the method for adjacent fluorophenol, it is characterized in that, described nitrosyl-sulfuric acid solution A is obtained with absorption liquid counter-current absorption in the multi-stage falling-film absorption tower of series connection by sulfurous gas.
6. pipe type continuously as claimed in claim 4 produces the method for adjacent fluorophenol, and it is characterized in that, the extraction agent described in step (3) is hydrophobic organic solvent.
7. pipe type continuously as claimed in claim 6 produces the method for adjacent fluorophenol, it is characterized in that, described extraction agent is one or more of methylene dichloride, toluene, dimethylbenzene, ether, propyl ether, ethyl acetate, propyl acetate, butylacetate, acetone, espeleton and mibk.
8. pipe type continuously as claimed in claim 4 produces the method for adjacent fluorophenol, and it is characterized in that, the temperature of raffinate acid solution low temperature crystallization is-15 ~ 10 DEG C.
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| CN106242939A (en) * | 2016-08-09 | 2016-12-21 | 浙江工业大学 | The method that difluorobenzene is prepared in the bis-diazotized reaction of a kind of tubular type |
| CN108358806A (en) * | 2018-01-15 | 2018-08-03 | 浙江山峪科技股份有限公司 | One inter-species acetaminophenol is continuously synthesizing to method |
| CN108558607A (en) * | 2018-05-03 | 2018-09-21 | 浙江解氏新材料股份有限公司 | A kind of high-efficiency synthesis method of neighbour's fluorophenol |
| CN109456150A (en) * | 2018-10-25 | 2019-03-12 | 浙江林江化工股份有限公司 | A kind of synthetic method of 3,4,5-Trifluoro phenol |
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| CN106242939A (en) * | 2016-08-09 | 2016-12-21 | 浙江工业大学 | The method that difluorobenzene is prepared in the bis-diazotized reaction of a kind of tubular type |
| CN106242939B (en) * | 2016-08-09 | 2018-11-13 | 浙江工业大学 | A kind of method that the bis-diazotized reaction of tubular type prepares difluorobenzene |
| CN108358806B (en) * | 2018-01-15 | 2020-09-18 | 江苏迪安化工有限公司 | Continuous synthesis method of m-acetamidophenol |
| CN108358806A (en) * | 2018-01-15 | 2018-08-03 | 浙江山峪科技股份有限公司 | One inter-species acetaminophenol is continuously synthesizing to method |
| CN108558607B (en) * | 2018-05-03 | 2021-05-18 | 浙江解氏新材料股份有限公司 | Efficient synthesis method of o-fluorophenol |
| CN108558607A (en) * | 2018-05-03 | 2018-09-21 | 浙江解氏新材料股份有限公司 | A kind of high-efficiency synthesis method of neighbour's fluorophenol |
| CN109456150A (en) * | 2018-10-25 | 2019-03-12 | 浙江林江化工股份有限公司 | A kind of synthetic method of 3,4,5-Trifluoro phenol |
| CN111978159A (en) * | 2020-07-15 | 2020-11-24 | 宁夏东吴农化股份有限公司 | Method for synthesizing para-fluorophenol by tubular reactor |
| CN112574002A (en) * | 2020-12-18 | 2021-03-30 | 浙江解氏新材料股份有限公司 | Method for preparing para-fluorophenol by using microchannel reactor |
| CN112778091A (en) * | 2020-12-30 | 2021-05-11 | 江苏恒沛药物科技有限公司 | Method for preparing o-fluorophenol from stable triazene intermediate |
| CN112778091B (en) * | 2020-12-30 | 2022-05-03 | 江苏恒沛药物科技有限公司 | Method for preparing o-fluorophenol from stable triazene intermediate |
| CN113845405A (en) * | 2021-10-18 | 2021-12-28 | 江苏快达农化股份有限公司 | Method for continuously synthesizing diflufenican intermediate m-trifluoromethylaniline |
| CN114349627A (en) * | 2022-01-25 | 2022-04-15 | 山东友道化学有限公司 | Preparation method of 2-methyl-3-hydroxybenzoic acid |
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Application publication date: 20160413 |