CN106905096A - A kind of method of continuous stream synthesizing phenol class compound - Google Patents

A kind of method of continuous stream synthesizing phenol class compound Download PDF

Info

Publication number
CN106905096A
CN106905096A CN201710167648.1A CN201710167648A CN106905096A CN 106905096 A CN106905096 A CN 106905096A CN 201710167648 A CN201710167648 A CN 201710167648A CN 106905096 A CN106905096 A CN 106905096A
Authority
CN
China
Prior art keywords
static mixer
formula
iii
solution
acid solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710167648.1A
Other languages
Chinese (zh)
Inventor
杜晓华
陈金沙
徐振元
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang University of Technology ZJUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CN201710167648.1A priority Critical patent/CN106905096A/en
Publication of CN106905096A publication Critical patent/CN106905096A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/02—Formation or introduction of functional groups containing oxygen of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a kind of method of the phenol compound shown in continuous stream synthesis type (III), carried out in two static mixers, tubular reactor and oil water separators being sequentially connected in series, comprised the following steps：Amino benzenes compounds shown in acid solution and formula (I) are pumped into static mixer A；In the static mixer B that the mixture of acid solution and formula (I) compound flows out from static mixer A, inflow is connected with static mixer A, sodium nitrite solution is also pumped into static mixer B, react the diazonium salt solution shown in production (II)；Formula (II) flows out from static mixer B, pump into the tubular reactor that is connected with static mixer B, and the oil water separator that then inflow is connected with tubular reactor obtains formula (III) compound after separation water phase.The present invention has that the reaction time is short, save solvent, the characteristics of high income, can solve problem present in diazotising hydrolysis phenol compound in batch tank reactor.

Description

A kind of method of continuous stream synthesizing phenol class compound
Technical field
The invention belongs to catalyst preparation field, and in particular to be a kind of continuous stream synthesizing phenol class compound Method.
Background technology
Phenol is important industrial chemicals, can manufacture dyestuff, medicine, phenolic resin, adhesive etc..Wherein catechol, right Benzenediol can make developer, phenol and the like can manufacture sterilization antiseptic, and in molecular biology test, phenol can be used to do Remove the reagent of isolating protein, the mixture and pentachlorophenol of phenol and cresols can be used for timber preservative, and the sodium salt of the latter is also The oncomelania in blood fluke epidemic-stricken area can be killed.
What the synthetic method document of phenol was provided has five kinds:Hydrogen peroxide oxidation process, alkylation process, electrolysis, diazonium Change Hydrolyze method, ether Hydrolyze method etc..
Wherein diazotising Hydrolyze method is the most conventional synthetic method of phenols, and raw material is easy to get, low cost, suitable extensive raw Produce.The method is industrially to apply to obtain widest method at present.But diazol is explosive, dangerous, Er Qiechong is mass produced Accessory substance is more when nitrogen salt is hydrolyzed, and the three wastes are more.
Based on above problems of the prior art and defect, a kind of new synthetic method need to be found and be applied to phenol In the synthesis of compound.
The content of the invention
It is an object of the invention to solve the problems, such as that synthesizing phenol class compound is produced in the prior art, there is provided a kind of new The method of synthesizing phenol class compound.
In order to achieve the above object, the present invention uses following technical scheme：
A kind of method of the phenol compound shown in continuous stream synthesis type (III), it is characterised in that the continuous stream synthesis The method of the phenol compound shown in formula (III) is in two static mixers, tubular reactor and water-oil separatings being sequentially connected in series Carried out in device, described method is comprised the following steps：
(1) amino benzenes compounds shown in acid solution and formula (I) are pumped into static mixer A, acid solution and phenyl amines Compound flow velocity is 12.2~608.2g/min, 1.0~50g/min, 0.6~50s of residence time, 0~50 DEG C of temperature；
(2) mixture of acid solution and the amino benzenes compounds shown in formula (I) from static mixer A outflows, flow into it is quiet In state blender A connected static mixer B, during sodium nitrite solution also to pump into static mixer B, sodium nitrite solution stream Speed is 1.5~72.8g/min, and temperature is 0~50 DEG C in static mixer B, and the residence time is 0.5~50s, reacts production (II) diazonium salt solution shown in；
(3) diazonium salt solution shown in formula (II) flows out from static mixer B, pumps into the pipe being connected with static mixer B In formula reactor, then 1~82mL/min of flow velocity, 80~100 DEG C of reaction temperature, 0.1~50min of residence time flows into and pipe The connected oil water separator of formula reactor, obtains the phenol compound shown in formula (III) after separation water phase.
In formula (I) or formula (II) or formula (III), R is C1~C8Alkyl, amino, hydroxyl, nitro, halogen ,-CF3Or-CO2H； The X is-HSO4, Cl or Br.
Further, in formula (I) or formula (II) or formula (III), R is preferably amino, hydroxyl, nitro, halogen or-CF3；The X Preferably-HSO4Or Cl.
Further, in amino benzenes compounds of the present invention, sodium nitrite solution Sodium Nitrite, acid solution during sour unit The amount ratio of the material of interior addition is 1：1.00~1.03：4~7.
Further, acid solution of the present invention is sulfuric acid solution, hydrochloric acid solution or HBr solution.
Further, sulfuric acid solution mass percentage concentration of the present invention is 10~60%；
Further, the mass percentage concentration of hydrochloric acid solution of the present invention is 10~40%；
Further, the mass percentage concentration of HBr solution of the present invention is 10~40%.
Further, the mass percentage concentration of sodium nitrite solution of the present invention is 10~40%.
Further, static mixer A of the present invention, static mixer B can be any static mixers, including the heart The static mixers such as type, straight type, SK types, SV types, SX types, SL types.
Further, tubular reactor of the present invention can be for static mixer, horizontal tube reactor, vertical tube type back should Device, coil pipe type reactor, U-shaped tubular reactor or multitube parallel tubular reactor.
Further, oil water separator of the present invention can be band-type oil-water separator or pipe type oil-water separator.
Beneficial effects of the present invention：Using the method for continuous stream synthesizing phenol class compound, diazo-reaction time 34s, The yield 93.6% of 12.5 DEG C of reaction temperature, phenol compound, compared to the diazo-reaction time that batch tank reacts 70min, 3 DEG C of reaction temperature, the yield 81.9% of phenol compound have obvious advantage, can solve batch tank Problem present in diazotising hydrolysis phenol compound in reactor, and various diazonium salt hydrolysis, fluorination, chlorine can be used for The reaction such as change and bromination.
Brief description of the drawings
Fig. 1 is flow chart of the invention.
Fig. 2 is the mass spectrogram of 3- bromophenols prepared by the embodiment of the present invention 11.
Fig. 3 is the mass spectrogram of 3- iodophenols prepared by the embodiment of the present invention 12.
Fig. 4 is the mass spectrogram of 3- amino phenols prepared by the embodiment of the present invention 13.
Specific embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in This.
Straight type static mixer A volumes as described below are all 8.2ml；Cardioid static mixer B volumes are all 8.2ml； Tubular reactor is that 5 volumes are the identical cardioid tubular reactor of 8.2ml and are in series.
Embodiment 1
At room temperature, the sulfuric acid solution electromagnetic dosing pump of mass percentage concentration 25% is pumped into the speed of 49.9g/min Straight type static mixer A, then pumps into straight type static state by 3-Aminotrifluorotoluene electromagnetic dosing pump with the speed of 4.1g/min Blender A, the heat conduction oil temperature of straight type static mixer A is set as 12.5 DEG C, and the natrium nitrosum of mass percentage concentration 30% is molten Liquid pumps into cardioid static mixer B, cardioid static mixer B with Hanbon-NP7010C efficient liquid phases pump with the speed of 6g/min Heat conduction oil temperature be set as 12.5 DEG C, diazonium salt solution is obtained after reaction.The heat conduction oil temperature of cardioid tubular reactor is set Be set to 88 DEG C, while diazonium salt solution is pumped into the speed cardioid of 1ml/min with Hanbon-NP7010C efficient liquid phases pump Tubular reactor, reaction solution enters cardioid oil water separator after reaction, collects 120min, finally gives fluoroform between oily liquids Base phenol 7.9g, purity 99.2%, yield 93.6%.1H NMR(CDCl3)δ:6.26 (s, 1H, OH), 7.07 (dd, J=2.4, 8.2Hz, 1H), 7.16 (s, 1H), 7.26 (d, J=7.8Hz, 1H), 7.38 (t, J=8.0Hz, 1H) .13C NMR (CDCl3) δ: 112.4 (q, J=3.9Hz), 118.1 (q, J=3.9Hz), 118.9 (s), 123.8 (q, J=270.6Hz), 130.4 (s), 132.2 (q, J=32.3Hz), 155.2.
Embodiment 2
At room temperature, the sulfuric acid solution electromagnetic dosing pump of mass percentage concentration 25% is pumped into the speed of 49.9g/min Straight type static mixer A, then pumps into straight type static state by 3-Aminotrifluorotoluene electromagnetic dosing pump with the speed of 4.1g/min The heat conduction oil temperature of blender A, straight type static mixer A is set as 0 DEG C, and the sodium nitrite solution of mass percentage concentration 30% is used Hanbon-NP7010C efficient liquid phases pump pumps into cardioid static mixer B with the speed of 6g/min, and cardioid static mixer B's leads Hot oil temperature is set as 0 DEG C, and diazonium salt solution is obtained after reaction.The heat conduction oil temperature of cardioid tubular reactor is set as 80 DEG C, while it is anti-that diazonium salt solution is pumped into tubular type with the speed cardioid of 82ml/min with Hanbon-NP7010C efficient liquid phases pump Device is answered, reaction solution enters cardioid oil water separator after reaction, collect 1min, finally give oily liquids m-trifluoromethyl phenol 1.5g, purity 99.2%, yield 26.3%.
Embodiment 3
At room temperature, the sulfuric acid solution electromagnetic dosing pump of mass percentage concentration 25% is pumped into the speed of 49.9g/min Straight type static mixer A, then pumps into straight type static state by 3-Aminotrifluorotoluene electromagnetic dosing pump with the speed of 4.1g/min The heat conduction oil temperature of blender A, straight type static mixer A is set as 0 DEG C, and the sodium nitrite solution of mass percentage concentration 30% is used Hanbon-NP7010C efficient liquid phases pump pumps into cardioid static mixer B with the speed of 6g/min, and cardioid static mixer B's leads Hot oil temperature is set as 0 DEG C, and diazonium salt solution is obtained after reaction.The heat conduction oil temperature of cardioid tubular reactor is set as 100 DEG C, while it is anti-that diazonium salt solution is pumped into tubular type with the speed cardioid of 1ml/min with Hanbon-NP7010C efficient liquid phases pump Device is answered, reaction solution enters cardioid oil water separator after reaction, collect 120min, finally give oily liquids m-trifluoromethyl phenol 4.8g, purity 99.2%, yield 57.1%.
Embodiment 4
At room temperature, the sulfuric acid solution electromagnetic dosing pump of mass percentage concentration 25% is pumped into the speed of 49.9g/min Straight type static mixer A, then pumps into straight type static state by 3-Aminotrifluorotoluene electromagnetic dosing pump with the speed of 4.1g/min Blender A, the heat conduction oil temperature of straight type static mixer A is set as 50 DEG C, the sodium nitrite solution of mass percentage concentration 30% Cardioid static mixer B is pumped into the speed of 6g/min with Hanbon-NP7010C efficient liquid phases pump, cardioid static mixer B's Heat conduction oil temperature is set as 50 DEG C, and diazonium salt solution is obtained after reaction.The heat conduction oil temperature of cardioid tubular reactor is set as 80 DEG C, while diazonium salt solution is pumped into tubular type with the speed cardioid of 1ml/min with Hanbon-NP7010C efficient liquid phases pump Reactor, reaction solution enters cardioid oil water separator after reaction, collects 120min, finally gives oily liquids m-trifluoromethyl benzene Phenol 3.1g, purity 99.2%, yield 36.9%.
Embodiment 5
At room temperature, the sulfuric acid solution electromagnetic dosing pump of mass percentage concentration 25% is pumped into the speed of 39.9g/min Straight type static mixer A, then pumps into straight type static state by 3-Aminotrifluorotoluene electromagnetic dosing pump with the speed of 4.1g/min Blender A, the heat conduction oil temperature of straight type static mixer A is set as 12.5 DEG C, and the natrium nitrosum of mass percentage concentration 30% is molten Liquid pumps into cardioid static mixer B, cardioid static mixer B with Hanbon-NP7010C efficient liquid phases pump with the speed of 6g/min Heat conduction oil temperature be set as 12.5 DEG C, diazonium salt solution is obtained after reaction.The heat conduction oil temperature of cardioid tubular reactor is set Be set to 88 DEG C, while diazonium salt solution is pumped into the speed cardioid of 1ml/min with Hanbon-NP7010C efficient liquid phases pump Tubular reactor, reaction solution enters cardioid oil water separator after reaction, collects 120min, finally gives fluoroform between oily liquids Base phenol 7.0g, purity 99.2%, yield 83.3%.
Embodiment 6
At room temperature, the sulfuric acid solution electromagnetic dosing pump of mass percentage concentration 25% is pumped into the speed of 69.9g/min Straight type static mixer A, then pumps into straight type static state by 3-Aminotrifluorotoluene electromagnetic dosing pump with the speed of 4.1g/min Blender A, the heat conduction oil temperature of straight type static mixer A is set as 12.5 DEG C, and the natrium nitrosum of mass percentage concentration 30% is molten Liquid pumps into cardioid static mixer B, cardioid static mixer B with Hanbon-NP7010C efficient liquid phases pump with the speed of 6g/min Heat conduction oil temperature be set as 12.5 DEG C, diazonium salt solution is obtained after reaction.The heat conduction oil temperature of cardioid tubular reactor is set Be set to 88 DEG C, while diazonium salt solution is pumped into the speed cardioid of 1ml/min with Hanbon-NP7010C efficient liquid phases pump Tubular reactor, reaction solution enters cardioid oil water separator after reaction, collects 120min, finally gives fluoroform between oily liquids Base phenol 7.4g, purity 99.2%, yield 88.1%.
Embodiment 7
At room temperature, the sulfuric acid solution electromagnetic dosing pump of mass percentage concentration 25% is pumped into the speed of 12.17g/min Straight type static mixer A, then pumps into straight type static state by 3-Aminotrifluorotoluene electromagnetic dosing pump with the speed of 1.0g/min Blender A, the heat conduction oil temperature of straight type static mixer A is set as 12.5 DEG C, and the natrium nitrosum of mass percentage concentration 30% is molten Liquid pumps into cardioid static mixer B, cardioid static mixing with Hanbon-NP7010C efficient liquid phases pump with the speed of 1.46g/min The heat conduction oil temperature of device B is set as 12.5 DEG C, and diazonium salt solution is obtained after reaction.By the heat conduction oil temperature of cardioid tubular reactor It is set as 88 DEG C, while with Hanbon-NP7010C efficient liquid phases pump by diazonium salt solution with the speed cardioid pump of 1ml/min Enter tubular reactor, reaction solution enters cardioid oil water separator after reaction, collect 120min, finally give trifluoro between oily liquids Methylphenol 2.6g, purity 99.2%, yield 31.0%.
Embodiment 8
At room temperature, the sulfuric acid solution electromagnetic dosing pump of mass percentage concentration 25% is pumped into the speed of 608.2g/min Straight type static mixer A, then pumps into 3-Aminotrifluorotoluene electromagnetic dosing pump straight type static state and mixes with the speed of 50g/min Clutch A, the heat conduction oil temperature of straight type static mixer A is set as 12.5 DEG C, the sodium nitrite solution of mass percentage concentration 30% Cardioid static mixer B, cardioid static mixer are pumped into the speed of 72.8g/min with Hanbon-NP7010C efficient liquid phases pump The heat conduction oil temperature of B is set as 12.5 DEG C, and diazonium salt solution is obtained after reaction.The heat conduction oil temperature of cardioid tubular reactor is set Be set to 88 DEG C, while diazonium salt solution is pumped into the speed cardioid of 1ml/min with Hanbon-NP7010C efficient liquid phases pump Tubular reactor, reaction solution enters cardioid oil water separator after reaction, collects 120min, finally gives fluoroform between oily liquids Base phenol 4.1g, purity 99.2%, yield 48.8%.
Embodiment 9
At room temperature, the hydrochloric acid solution electromagnetic dosing pump of mass percentage concentration 25% is pumped into the speed of 18.7g/min Straight type static mixer A, then pumps into straight type static state by 3-Aminotrifluorotoluene electromagnetic dosing pump with the speed of 4.1g/min Blender A, the heat conduction oil temperature of straight type static mixer A is set as 12.5 DEG C, and the natrium nitrosum of mass percentage concentration 30% is molten Liquid pumps into cardioid static mixer B, cardioid static mixer B with Hanbon-NP7010C efficient liquid phases pump with the speed of 6g/min Heat conduction oil temperature be set as 12.5 DEG C, diazonium salt solution is obtained after reaction.The heat conduction oil temperature of cardioid tubular reactor is set Be set to 88 DEG C, while diazonium salt solution is pumped into the speed cardioid of 1ml/min with Hanbon-NP7010C efficient liquid phases pump Tubular reactor, reaction solution enters cardioid oil water separator after reaction, collects 120min, finally gives fluoroform between oily liquids Base phenol 7.8g, purity 99.2%, yield 92.7%.
Embodiment 10
At room temperature, the sulfuric acid solution electromagnetic dosing pump of mass percentage concentration 25% is pumped into the speed of 50.1g/min Straight type static mixer A, then pumps into straight type static mixer by m-fluoroaniline electromagnetic dosing pump with the speed of 2.84g/min The heat conduction oil temperature of A, straight type static mixer A is set as 12.5 DEG C, and the sodium nitrite solution of mass percentage concentration 30% is used Hanbon-NP7010C efficient liquid phases pump pumps into cardioid static mixer B with the speed of 6g/min, and cardioid static mixer B's leads Hot oil temperature is set as 12.5 DEG C, and diazonium salt solution is obtained after reaction.The heat conduction oil temperature of cardioid tubular reactor is set as 92 DEG C, while diazonium salt solution is pumped into cardioid tubular type with the speed of 1ml/min with Hanbon-NP7010C efficient liquid phases pump Reactor, reaction solution enters cardioid oil water separator after reaction, collects 120min, finally gives and obtains oily liquids m fluorophenol 6.7g, purity 99.5%, yield 94.3%.1H NMR(CDCl3)δ:6.37(s,1H),6.55-6.57(m,1H),6.59- 6.66(m,2H),7.12-7.19(m,1H).
Embodiment 11
At room temperature, the sulfuric acid solution electromagnetic dosing pump of mass percentage concentration 25% is pumped into the speed of 49.9g/min Straight type static mixer A, then pumps into straight type static mixer by m-bromoaniline electromagnetic dosing pump with the speed of 4.4g/min The heat conduction oil temperature of A, straight type static mixer A is set as 12.5 DEG C, and the sodium nitrite solution of mass percentage concentration 30% is used Hanbon-NP7010C efficient liquid phases pump pumps into cardioid static mixer B with the speed of 6g/min, and cardioid static mixer B's leads Hot oil temperature is set as 12.5 DEG C, and diazonium salt solution is obtained after reaction.The heat conduction oil temperature of cardioid tubular reactor is set as 90 DEG C, while diazonium salt solution is pumped into cardioid tubular type with the speed of 1ml/min with Hanbon-NP7010C efficient liquid phases pump Reactor, reaction solution enters cardioid oil water separator after reaction, collects 120min, finally gives and obtains m -bromoacetophenone 8.1g, pure Degree 99.2%, yield 93.8%.
Embodiment 12
At room temperature, 25% sulfuric acid solution electromagnetic dosing pump is pumped into straight type static mixing with the speed of 50.2g/min Device A, then pumps into straight type static mixer A by an Iodoaniline electromagnetic dosing pump with the speed of 5.6g/min, and straight type is static mixed The heat conduction oil temperature of clutch A is set as 10.0 DEG C, 30% sodium nitrite solution with Hanbon-NP7010C efficient liquid phases pump with The speed of 6g/min pumps into cardioid static mixer B, and the heat conduction oil temperature of cardioid static mixer B is set as 10.0 DEG C, reaction After obtain diazonium salt solution.The heat conduction oil temperature of cardioid tubular reactor is set as 88 DEG C, while using Hanbon-NP7010C Diazonium salt solution is pumped into cardioid tubular reactor by efficient liquid phase pump with the speed of 1ml/min, and reaction solution enters the heart after reaction Type oil water separator, collects 120min, finally gives and obtains an iodophenol 11.4g, purity 99.1%, yield 92.5%.
Embodiment 13
At room temperature, 25% sulfuric acid solution is pumped into static mixer A with the speed of 50.2g/min, then by isophthalic two Amine pumps into static mixer A with the speed of 2.77g/min, and the heat conduction oil temperature of micro passage reaction is set as 10.0 DEG C, 30% Sodium nitrite solution efficient liquid phase pump static mixer B, the heat conduction oil temperature of static mixer B are pumped into the speed of 6g/min Degree is set as 10.0 DEG C, and diazonium salt solution is obtained after reaction.The heat conduction oil temperature of tubular reactor is set as 90 DEG C, while with Diazonium salt solution is pumped into tubular reactor by Hanbon-NP7010C efficient liquid phases pump with the speed of 1ml/min, after anti-reaction Reaction solution enters oil water separator, collects 120min, finally gives and obtains m-aminophenol 6.5g, purity 99.3%, yield 92.8%.
Embodiment 14
At room temperature, 25% sulfuric acid solution is pumped into static mixer A with the speed of 49.7g/min, then the nitro by between Aniline pumps into static mixer A with the speed of 3.5g/min, and the heat conduction oil temperature of micro passage reaction is set as 12.5 DEG C, 30% Sodium nitrite solution efficient liquid phase pump static mixer B, the heat conduction oil temperature of static mixer B are pumped into the speed of 6g/min Degree is set as 12.5 DEG C, and diazonium salt solution is obtained after reaction.The heat conduction oil temperature of tubular reactor is set as 90 DEG C, while with Diazonium salt solution is pumped into tubular reactor by Hanbon-NP7010C efficient liquid phases pump with the speed of 1ml/min, anti-after reaction Answer liquid to enter oil water separator, collect 120min, finally give and obtain metanitrophenol 6.7g, purity 99.2%, yield 92.3%.1H NMR(CDCl3):δ7.82-7.79(m,1H),7.73(t,1H),7.41(t,1H),7.23-7.20(m,1H), 6.15(s,1H).
Embodiment 15
At room temperature, 25% sulfuric acid solution is pumped into static mixer A with the speed of 50.2g/min, then the hydroxyl by between Aniline pumps into static mixer A with the speed of 2.8g/min, and the heat conduction oil temperature of micro passage reaction is set as 12.5 DEG C, 30% Sodium nitrite solution efficient liquid phase pump static mixer B, the heat conduction oil temperature of static mixer B are pumped into the speed of 6g/min Degree is set as 12.5 DEG C, and diazonium salt solution is obtained after reaction.The heat conduction oil temperature of tubular reactor is set as 90 DEG C, while with Diazonium salt solution is pumped into tubular reactor by Hanbon-NP7010C efficient liquid phases pump with the speed of 1ml/min, anti-after reaction Answer liquid to enter oil water separator, collect 120min, finally give and obtain resorcinol 5.2g, purity 99.3%, yield 91.8%. 1H NMR(CD3OD):δ6.96-6.90(m,1H),6.27-6.24(m,3H)。

Claims (8)

1. a kind of method of the phenol compound shown in continuous stream synthesis type (III), it is characterised in that the continuous stream synthesis type (III) method of the phenol compound shown in is in two static mixers, tubular reactor and oil water separators being sequentially connected in series In carry out, described method is comprised the following steps：
(1) amino benzenes compounds shown in acid solution and formula (I) are pumped into static mixer A, acid solution and amino benzenes compounds Flow velocity is 12.2~608.2g/min, 1.0~50g/min, 0.6~50s of residence time, 0~50 DEG C of temperature；
(2) mixture of acid solution and the amino benzenes compounds shown in formula (I) from static mixer A outflows, flow into and mixed with static state In clutch A connected static mixer B, sodium nitrite solution is also pumped into static mixer B, sodium nitrite solution flow velocity is 1.5~72.8g/min, temperature is 0~50 DEG C in static mixer B, and the residence time is 0.5~50s, reacts production (II) institute The diazonium salt solution for showing；
(3) diazonium salt solution shown in formula (II) from static mixer B outflow, pump into it is anti-with the tubular type that static mixer B is connected Answer in device, then 1~82mL/min of flow velocity, 80~100 DEG C of reaction temperature, 0.1~50min of residence time flows into anti-with tubular type The oil water separator for answering device connected, obtains the phenol compound shown in formula (III) after separation water phase.
In formula (I) or formula (II) or formula (III), R is C1~C8Alkyl, amino, hydroxyl, nitro, halogen ,-CF3Or-CO2H；The X For-HSO4, Cl or Br.
2. the method for the phenol compound shown in continuous stream synthesis type (III) as claimed in claim 1, it is characterised in that：Formula (I) or in formula (II) or formula (III), R is amino, hydroxyl, nitro, halogen or-CF3；The X is-HSO4Or Cl.
3. the method for the phenol compound shown in continuous stream synthesis type (III) as claimed in claim 1, it is characterised in that：Institute The amount ratio for stating the material added in the sour unit interval in amino benzenes compounds, sodium nitrite solution Sodium Nitrite, acid solution is 1：1.00~1.03：4~7.
4. the method for the phenol compound shown in continuous stream synthesis type (III) as claimed in claim 1, it is characterised in that：Institute Acid solution is stated for sulfuric acid solution, hydrochloric acid solution or HBr solution.
5. the method for the phenol compound shown in continuous stream synthesis type (III) as claimed in claim 3, it is characterised in that：Institute It is 10~60% to state sulfuric acid solution mass percentage concentration.
6. the method for the phenol compound shown in continuous stream synthesis type (III) as claimed in claim 3, it is characterised in that：Institute The mass percentage concentration for stating hydrochloric acid solution is 10~40%.
7. the method for the phenol compound shown in continuous stream synthesis type (III) as claimed in claim 3, it is characterised in that：Institute The mass percentage concentration for stating HBr solution is 10~40%.
8. the method for the phenol compound shown in continuous stream synthesis type (III) as claimed in claim 1, it is characterised in that：Institute The mass percentage concentration for stating sodium nitrite solution is 10~40%.
CN201710167648.1A 2017-03-21 2017-03-21 A kind of method of continuous stream synthesizing phenol class compound Pending CN106905096A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710167648.1A CN106905096A (en) 2017-03-21 2017-03-21 A kind of method of continuous stream synthesizing phenol class compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710167648.1A CN106905096A (en) 2017-03-21 2017-03-21 A kind of method of continuous stream synthesizing phenol class compound

Publications (1)

Publication Number Publication Date
CN106905096A true CN106905096A (en) 2017-06-30

Family

ID=59194524

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710167648.1A Pending CN106905096A (en) 2017-03-21 2017-03-21 A kind of method of continuous stream synthesizing phenol class compound

Country Status (1)

Country Link
CN (1) CN106905096A (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107903187A (en) * 2017-11-01 2018-04-13 新华制药（寿光）有限公司 A kind of aniline high temperature diazotization process
CN108191611A (en) * 2018-02-05 2018-06-22 衢州鑫锐化工科技有限公司 A kind of 2,5- xylenols are continuously synthesizing to method
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
CN109422659A (en) * 2017-08-23 2019-03-05 中国石油化工股份有限公司 A kind of method that m-phenylene diamine (MPD) hydrolysis prepares meta-aminophenol
CN110818533A (en) * 2019-09-04 2020-02-21 浙江巍华新材料股份有限公司 Preparation method of m-trifluoromethylphenol
CN111302954A (en) * 2020-04-29 2020-06-19 青岛科技大学 Preparation process of m-aminophenol and equipment used in preparation process
CN111704555A (en) * 2020-06-17 2020-09-25 爱斯特（成都）生物制药股份有限公司 Method for synthesizing 4-methoxy-2-nitroaniline by adopting continuous flow reactor
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
CN112250548A (en) * 2020-11-10 2021-01-22 上海惠和化德生物科技有限公司 Continuous reaction system and method for preparing substituted phenol
CN113024409A (en) * 2021-03-09 2021-06-25 扬州大学 Method for preparing diazo compound by using nitrogen oxide and primary arylamine as raw materials
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
US20220119330A1 (en) * 2020-10-19 2022-04-21 Inner Mongolia Sheng Tang International Mongolian Medicine Research Institute Co., Ltd. Method for preparing resorcinol through micro-channel reaction

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5344489A (en) * 1976-10-05 1978-04-21 Dainippon Ink & Chem Inc Nematic liquid crystal composition
US4355186A (en) * 1980-06-27 1982-10-19 Hoechst Aktiengesellschaft Process for the preparation of 4-phenoxy-phenols
CN105392764A (en) * 2013-07-27 2016-03-09 威尔化学法兰克福有限责任公司 Process for the preparation of phenols
CN106220474A (en) * 2016-06-27 2016-12-14 衢州学院 A kind of new method preparing paracresol

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5344489A (en) * 1976-10-05 1978-04-21 Dainippon Ink & Chem Inc Nematic liquid crystal composition
US4355186A (en) * 1980-06-27 1982-10-19 Hoechst Aktiengesellschaft Process for the preparation of 4-phenoxy-phenols
CN105392764A (en) * 2013-07-27 2016-03-09 威尔化学法兰克福有限责任公司 Process for the preparation of phenols
CN106220474A (en) * 2016-06-27 2016-12-14 衢州学院 A kind of new method preparing paracresol

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109422659A (en) * 2017-08-23 2019-03-05 中国石油化工股份有限公司 A kind of method that m-phenylene diamine (MPD) hydrolysis prepares meta-aminophenol
CN107903187A (en) * 2017-11-01 2018-04-13 新华制药（寿光）有限公司 A kind of aniline high temperature diazotization process
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
CN108358806B (en) * 2018-01-15 2020-09-18 江苏迪安化工有限公司 Continuous synthesis method of m-acetamidophenol
CN108191611A (en) * 2018-02-05 2018-06-22 衢州鑫锐化工科技有限公司 A kind of 2,5- xylenols are continuously synthesizing to method
CN110818533B (en) * 2019-09-04 2022-04-12 浙江巍华新材料股份有限公司 Preparation method of m-trifluoromethylphenol
CN110818533A (en) * 2019-09-04 2020-02-21 浙江巍华新材料股份有限公司 Preparation method of m-trifluoromethylphenol
EP4029849A4 (en) * 2019-09-04 2023-10-25 Zhejiang Weihua New Material Co., Ltd. Method for preparing m-trifluoromethylphenol
WO2021042721A1 (en) 2019-09-04 2021-03-11 浙江巍华新材料股份有限公司 Method for preparing m-trifluoromethylphenol
CN111302954A (en) * 2020-04-29 2020-06-19 青岛科技大学 Preparation process of m-aminophenol and equipment used in preparation process
CN111704555A (en) * 2020-06-17 2020-09-25 爱斯特（成都）生物制药股份有限公司 Method for synthesizing 4-methoxy-2-nitroaniline by adopting continuous flow reactor
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
US20220119330A1 (en) * 2020-10-19 2022-04-21 Inner Mongolia Sheng Tang International Mongolian Medicine Research Institute Co., Ltd. Method for preparing resorcinol through micro-channel reaction
US11760709B2 (en) * 2020-10-19 2023-09-19 Inner Mongolia Sheng Tang International Mongolian Method for preparing resorcinol through micro-channel reaction
CN112250548A (en) * 2020-11-10 2021-01-22 上海惠和化德生物科技有限公司 Continuous reaction system and method for preparing substituted phenol
CN113024409A (en) * 2021-03-09 2021-06-25 扬州大学 Method for preparing diazo compound by using nitrogen oxide and primary arylamine as raw materials
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

Similar Documents

Publication Publication Date Title
CN106905096A (en) A kind of method of continuous stream synthesizing phenol class compound
CN110818533B (en) Preparation method of m-trifluoromethylphenol
JP6366148B2 (en) Continuous production and reaction of diazo compounds
CN111519204B (en) Method for preparing N- (5-chloro-8-quinolyl) benzamide compound by adopting electrochemical microchannel reaction device
JP2002038043A (en) Preparation of disazo condensation pigment in microreactor
CN104437235B (en) Long chain cation gemini surfactant and preparation method thereof
CN110372526A (en) A kind of preparation method of 3- methyl-2-amino benzoic acid
CN106831407B (en) A kind of synthetic method of α-chlorpromazine chloride
CN102060717B (en) The synthetic method of the bromophenol of 3 amino 4
CN106045803B (en) A kind of green bionic catalysis nitration method of phenolic compound
CN103391912A (en) Method for the hydroxylation of phenols and phenol ethers
CN104610012B (en) A kind of synthetic method of cold labeling halogeno-benzene
US20180334421A1 (en) Synthesis Method of 3,4-hexanedione
CN105541667B (en) The method that continuous conduit metaplasia produces CLT acid itrated compound
CN106748769B (en) A kind of polysubstituted 3- phenyl phenol derivatives and preparation method thereof
CN106220474A (en) A kind of new method preparing paracresol
US10968156B2 (en) Process for the manufacturing of a 3-halopropionyl halide in a flow reactor
CN107793295A (en) A kind of preparation method of 3,5 difluorophenol
CN109422663B (en) Method for continuous flow synthesis of quaternary ammonium salt
CN105541668B (en) A kind of method of duct type continuous production CLT acid chloride
CN107827850A (en) A kind of acid-base indicator and its preparation method and application
CN105418391B (en) A kind of preparation method of p-trifluoromethyl benzaldehyde
CN106278837A (en) The Preparation Method And Their Intermediate of o-trifluoromethyl-4-halogenated benzaldehyde
CN107522595A (en) A kind of process for preparing resorcinol
CN108191611A (en) A kind of 2,5- xylenols are continuously synthesizing to method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20170630

RJ01 Rejection of invention patent application after publication