CN105175235A - Method of preparing aromatic aldehyde and ketone through continuously oxidizing aromatic alcohol by adopting tubular reactor - Google Patents
Method of preparing aromatic aldehyde and ketone through continuously oxidizing aromatic alcohol by adopting tubular reactor Download PDFInfo
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- CN105175235A CN105175235A CN201510573405.9A CN201510573405A CN105175235A CN 105175235 A CN105175235 A CN 105175235A CN 201510573405 A CN201510573405 A CN 201510573405A CN 105175235 A CN105175235 A CN 105175235A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
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- 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
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- B01J2208/06—Details of tube reactors containing solid particles
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Abstract
The invention provides a method of preparing aromatic aldehyde and ketone through continuously oxidizing aromatic alcohol by adopting a tubular reactor, and belongs to the technical field of organic synthesis processes. According to the method, an aromatic alcohol compound is taken as a raw material; 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) is taken as a catalyst; pypocholoride is taken as an oxidizing agent; nitrogenous organic matter is taken as a solvent. The method is a process technology that the aromatic alcohol is continuously oxidized in the tubular reactor to prepare the aromatic aldehyde and ketone. The method has the characteristics of mild conditions, short reaction time, high raw material utilization ratio, being capable of realizing effective control in the reaction process, being safe and reliable, and continuous operation and high production efficiency.
Description
Technical field
The invention belongs to organic synthesis Technology field, relate to a kind of method being prepared aromatic aldehyde ketone under liquid-phase reaction condition by aromatic alcohol continuous oxidation, more specifically be take aromatic alcohol compound as substrate, hypochlorite is oxygenant, 2,2,6, the TEMPO of 6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) or support is catalyzer, and hypochlorite is oxygenant, and in the tubular reactor of different structure, continuous oxidationization produces the method for aromatic aldehyde ketone.
Background technology
Carbonyl compounds is in chemical industry synthesis field extensive application, and aromatic series aldehyde ketone can be applicable to the chemical industries such as medicine, agricultural chemicals, food, essence and flavoring agent as important industrial chemicals.The annual carbonyl compound produced in the whole world is more than 1,000,000 tons according to statistics, and wherein most carbonyl compound gets from alcohol oxidation.
Prepare the existing a large amount of report of Study on Process of aldehyde ketone about alcohol oxidation, and achieve a lot of application achievements.Alcohol is transformed into the carbonyl compound such as corresponding aldehyde, ketone, mainly adopts the method for stoichiometry oxidation traditionally.The oxidant species of application is a lot, as: chromium reagent manganese reagent and other transition metal oxide, hypervalent iodine reagent, Sha Ruite reagent (chromic anhydride-bis-pyridine complex), Jones reagent (dilution heat of sulfuric acid of chromic anhydride), Fei Zina and Mo Fate reagent (DMSO-DCC) etc., these methods need equivalent or excessive oxygenant usually, and cost is very high.Although these methods are simple to operate, speed of response fast, easily there is over oxidation and generate more by product in reaction substrate, the yield of target product is lower, and bring larger difficulty to later separation treating processes, easily causes serious environmental pollution.
1987, Anelli found to use 4-CH
3o-TEMPO is catalyzer, when KBr is promotor, can quickly catalysis hypochlorite to oxidation (AnelliPL, the BiffiC of alcohol, MontanariF, etal.J.Org.Chem, 1987,52,2559-2562), the selectivity of the corresponding product aldehydes or ketones obtained is very high; Research afterwards finds that TEMPO and KBr can serve the same role.Usually with CH
2c1
2for solvent, add amount of substrate 1%(mol number) TEMPO and 10%(mol number) NaBr or KBr, and than substrate little over amount NaOCl solution, react at pH=8.6,0-15 DEG C.Under this condition, primary, secondary alcohol can Quick Oxidation be optionally corresponding aldehydes or ketones.Relative to the transition metal-catalyzed oxygenant TEMPO catalyzer of costliness, there is low price, be easy to remove, the advantage such as environmentally friendly.
Since TEMPO reagent in 1987 is found the katalysis that alcohol is oxidized, this method for oxidation has obtained extensive concern and application, and substitutes traditional oxidising agent gradually as oxidising agents such as PCC, PDC, Jones reagent.CN102617319 discloses a kind of method being oxidized to aldehydes or ketones by alcohol, the method take TEMPO as catalyzer, iodine is promotor, and the hydrogen peroxide trimethyl carbinol is oxygenant, reacts and different types of alcohol was oxidized to corresponding aldehydes or ketones in 2-24 hour at 60-100 DEG C.The oxygenant environmental protection environmental pollution that the method adopts is little, but the method still adopts intermittent reaction, in reaction process, oxygenant needs slowly to be added dropwise in reactor, mass-and heat-transfer weak effect between reactant, oxygenant stability is bad, easily causes and " temperature runaway " phenomenon occurs because local temperature is too high.And it is large to there is oxygenant usage quantity, selectivity of product is low, long reaction time, and catalyzer is difficult to the shortcomings such as recovery.
For the series of problems that above-mentioned processing method exists, have not yet to see more comprehensive solution.Some investigators of drawback for rhythmic reaction operating method propose to adopt fixed-bed reactor or microreactor to improve its production efficiency to the continuous prodution realizing the oxidation of TEMPO catalytic alcohol.2009, supported AO-TEMPO is filled in fluoroplastics tubular reactor by Bogdan etc., by the mode of injection, substrate alcohol, promotor and oxidizing agent sodium hypochlorite's solution are squeezed into " Y " type hybrid channel and then enter fixed-bed reactor, under the catalysis of AO-TEMPO, obtain corresponding aldehydes or ketones.Refer to reference: BogdanA, McquadeT.BeilsteinJ.Org.Chem.2009,5,17; FerstlW.etal.Chem.Eng.J.2008,135S, S292; Fritz-LanghalsE.Org.Proc.Res.Dev.2005,9,577-582.2012, Leduc, AndrewB etc. in tubular reactor with ethyl acetate or methyl alcohol for solvent, chlorine bleach liquor is oxygenant, and Tetrabutyl amonium bromide is promotor, in 20-30min, alcohol is oxidized to corresponding aldehyde ketone or ester at ambient temperature.Refer to reference: LeducAndrewB.JamisonTimothyF.Org.Proc.Res.Dev.2012,16 (5), 1082-1089.Although achieve the continuous prodution of alcohol oxidation in the above-mentioned methods, mass-and heat-transfer weak effect between reactant, the shortcoming that oxidant utilization is low is effectively solved not yet.In above-mentioned reaction process, the usage quantity of oxygenant is generally the 2-3 of substrate alcohol molar weight doubly, and the selectivity of target product and yield are also corresponding lower.In order to solve the problem of mass transfer in reaction system, usually need the method adding phase-transfer catalyst or increase quantity of solvent to promote the mass transfer between reactant.But adding phase-transfer catalyst or increasing quantity of solvent to make reactive component complicated, and increase the incidence of side reaction, the later separation purification burden also having increased the weight of product makes production cost significantly increase.
Along with deepening continuously of people's research, the recovery and the recycling that realize TEMPO catalyzer reduce another important channel that alcohol is oxidized to corresponding aldehyde ketone production cost.US6995291 discloses the supported TEMPO catalyzer (PIPO) of a kind of employing and replaces TEMPO catalyzer in batch still, carry out the catalyzed oxidation of alcohol, wherein the add-on of PIPO is 0.02 ~ 0.1 molar equivalent of substrate alcohol, the add-on of promotor Sodium Bromide is 0 ~ 0.05 molar equivalent of substrate alcohol, and the add-on of clorox is 0.9 ~ 2.5 molar equivalent of substrate alcohol.The method achieves recovery and the recycling of catalyzer by the load of catalyzer, effectively reduces the production cost of target product.
The above method is prepared aldehyde ketone from different angles and is optimized to alcohol oxidation and improves, but still there are some problems and need to solve: in large-scale production, first still mainly adopt batch still batch to produce.Secondly still there is mass-and heat-transfer weak effect in the above-mentioned methods, oxidant utilization is low, and easily because of local superheating, the shortcomings such as " temperature runaway " phenomenon occur, this is also cause the usage quantity of oxygenant in above process larger, side reaction increases, the major cause that target product selectivity, yield are low.And utilize the Continuous Flow tubular reactor of ad hoc structure to carry out the continuous oxidation synthesis aldehyde ketone of alcohol, many deficiencies that can many-sidedly solve existing Technology and exist.
Adopt the Continuous Flow tubular reactor of ad hoc structure can control effectively to the mixing of reaction mass and mass transfer, heat transfer process.By the contact area effectively increased between reactant its mass-and heat-transfer effect can be strengthened to the design of pipeline configuration and size, accelerate speed of reaction Reaction time shorten, and improve the utilization ratio of oxygenant, reduce the usage quantity of oxygenant and avoid the use of promotor, solving " temperature runaway " phenomenon produced because of local superheating in reaction process simultaneously.By to the length of tubular reactor and the control of reaction time, can the distribution of raw material and product be made further more to optimize controlled; Can realize substrate alcohol and oxygenant by regulating the flow velocity of feedstock pump to enter tubular reactor in proportion and carry out reaction and greatly reduce back-mixing, further reduce the generation of side reaction, the stability of oxygenant and the selectivity of target product also significantly improve.The present invention adopt the tubular reactor of ad hoc structure to carry out method that aromatic alcohol continuous oxidation prepares aromatic aldehyde ketone has unrivaled advantage relative to conventional batch production method, and can be its industrialization quantity-produced and improve an important approach is provided.
Summary of the invention
The present invention is directed to the deficiency of above existence, provide a kind of method being prepared by aromatic alcohol continuous oxidation aromatic aldehyde ketone in tubular reactor.Present method reaction times is short, and production efficiency is high, and mass transfer, heat transfer are optimized greatly, and reaction process is stablized controlled more.Further object of the present invention is, by processing method of the present invention, realizes stablizing of alcohol continuous oxidation controlled, reduces the generation of by product.By the strengthening of mass-and heat-transfer process and the effective rate of utilization of process optimization raising reaction mass, the usage quantity of further reduction oxygenant and catalyzer and avoid the use of promotor in reaction process, thus effectively save production cost and then improve existing industrialized preparing process.
For achieving the above object, the technical solution used in the present invention is:
Adopt the tubular reactor of special construction that aromatic alcohol continuous oxidation is prepared a method for aromatic aldehyde ketone, carry out according to following step:
(1) take aromatic alcohol compound as substrate, hypochlorite is oxygenant, 2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) is catalyzer, itrogenous organic substance is solvent, and in the tubular reactor of various combination structure, continuous oxidation prepares aromatic aldehyde ketone.
(2) first at room temperature, substrate aromatic alcohol compound and nitrogenous organic solvent are uniformly mixed, then TEMPO and hypochlorite solutions are uniformly mixed and form composite catalytic oxidation agent and be adjusted to required pH value with acid.Two strands of materials are squeezed into continuously through volume pump respectively and after preheating mixing, are entered reaction zone in tubular reactor and react, and temperature of reaction is controlled by outer loop heat-exchange system.
(3) method by regulating flow velocity and meter to weigh controls the mol ratio of reaction mass, is controlled the residence time of mixing of materials reaction by the caliber size and length changing tubular reactor.After completion of the reaction, product flows out from reactor end and enters holding tank, and enter last handling process, product obtains target product after fractionation by distillation purifying, and wherein the yield of target product can reach 90.5%-96.7%.
Wherein said alcohol compound has following structure:
Wherein, R
1be selected from the one in halogen, methoxyl group, nitro, methyl, hydrogen.R
2be selected from the alkyl of C1-C8, hydrogen.
Wherein said catalyzer is the TEMPO of 2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) or support, and the mol ratio of its consumption and substrate aromatic alcohol compound is at (0.005-0.03): 1, and wherein preferred molar ratio is (0.005-0.015): 1.
Wherein said hypochlorite comprises: clorox, potassium hypochlorite, Losantin, and its strength of solution is 0.3-1.8mol/L preferred concentration is 0.5-1.2mol/L, preferable ph scope 6-9.The preferred molar ratio of hypochlorite and substrate aromatic alcohol compound is at (1.0-1.5): 1.
Wherein said itrogenous organic substance solvent comprises: acetonitrile, N, N ,-dimethyl formamide, N, N ,-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone.Wherein the volume ratio of solvent and substrate aromatic alcohol compound is at (5-15): 1.
Wherein said temperature of reaction is-10-50 DEG C, and preferable reaction temperature is 0-25 DEG C, and reaction time is 60s-180s.
In further technical scheme, first have neither part nor lot in the oxygenant of reaction after completion of the reaction with Sulfothiorine or S-WAT cancellation, then by organic solvent extraction, after fractionation by distillation purifying, obtain target product.
In technique scheme, described reactive system comprises the difference in functionality regions such as raw material storage tank, reaction zone, product collection district.Channel of reactor structure comprises: pipe once-through type channel architecture, cake formula pulse diameter varied narrow rectangular tube road structure, oblique side's cake formula pulse diameter varied narrow rectangular tube road structure, the HeartCell channel architecture of mixed type cake formula narrow rectangular tube road structure and Corning of strengthening.
The present invention has the following advantages:
1, the present invention adopts a kind of mode of production of serialization, and the reaction times is short, and reaction conditions is gentle, and process safety is controlled, and production efficiency is high.
2, the present invention is by adopting the tubular reactor made of different structure, can realize the effective control to reaction process, make reaction product rest on aldehyde ketone one step.
3, by significantly improve the utilization ratio of its speed of reaction and raw material to mass transfer, heat transfer intensification in reaction process, and effectively reduce the usage quantity of oxygenant and catalyzer, and avoid the use of promotor, production cost is effectively saved.
4, the present invention is easy and simple to handle, applied widely, and produce flexibly, the parallel connection by reaction unit expands the scale of production.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that aromatic alcohol continuous oxidation of the present invention prepares aromatic aldehyde ketone.
Fig. 2 is Continuous Flow tubular reactor setting drawing used in the present invention: 1,2-head tank, 3,4-raw material volume pump, 5,6-preheating zone, 7,8-reaction zone, and 9-product cancellation collecting region.
Fig. 3 is tubular reactor channel architecture schematic diagram used in the present invention, wherein a-once-through type channel architecture, b-cake formula pulse diameter varied narrow rectangular tube road, c-oblique side's cake formula pulse diameter varied narrow rectangular tube road, d-strengthens mixed type cake formula narrow rectangular tube road, the HeartCell structure microchannel of e-Corning.
Embodiment
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
embodiment 1
(1) device: with reference to the mode of connection of Fig. 2 determination tubular reactor, conduit types is: (3a) PFA pipe passageway, and duct length is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil or water.
(2) substrate p-methoxybenzyl alcohol, stirring solvent are mixed, the mixed solution of catalyzer and clorox is adjusted to required pH value, input in head tank 1,2 respectively.Then two strands of materials pump in tubular reactor by volume pump 3,4, first through preheating zone 5,6 preheating and then enter reaction zone and carry out hybrid reaction.Preheating temperature and the temperature of reaction of reactive system are set as-10 DEG C.Wherein, 2,2,6, its consumption of TEMPO catalyzer of 6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) or support and the mol ratio of p-methoxybenzyl alcohol are 0.005: 1, the volume ratio of p-methoxybenzyl alcohol and organic solvent acetonitrile is 1: 5, and chlorine bleach liquor's pH value is 6 concentration is 1.8mol/L.By regulating the flow rate control p-methoxybenzyl alcohol of volume pump and the mol ratio of clorox to be 1: 1.5, reaction time is 90s.React after product and entered holding tank from reactor outlet continuous discharge, added Sulfothiorine and carry out cancellation.Analyze through GC, raw material p-methoxybenzyl alcohol transformation efficiency is 98.3%, and the yield of aubepine is 95.6%.
embodiment 2
(1) device: with reference to the mode of connection of Fig. 2 determination tubular reactor, conduit types is: (3a+3b) once-through type passage+cake formula pulse diameter varied narrow rectangular tube road, duct length is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil or water.
(2) substrate is mixed fluorophenyl methanol, stirring solvent, the mixed solution of catalyzer and clorox is adjusted to required pH value, input in head tank 1,2 respectively.Then two strands of materials pump in tubular reactor by volume pump 3,4, first through preheating zone 5,6 preheating and then enter reaction zone and carry out hybrid reaction.The preheating temperature of reactive system and temperature of reaction are set as 0 DEG C.Wherein, 2,2, the TEMPO catalyzer of 6,6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) or support, its consumption be 0.03: 1 to the mol ratio of fluorophenyl methanol, to fluorophenyl methanol and organic solvent N, N, the volume ratio of-dimethyl formamide is 1: 10, and chlorine bleach liquor's pH value is 8 concentration is 0.3mol/L.By regulating the mol ratio of flow rate control to fluorophenyl methanol and clorox of volume pump to be 1: 1.0, reaction time is 180s.React after product and entered holding tank from reactor outlet continuous discharge, added Sulfothiorine and carry out cancellation.Analyze through GC, raw material is 97.8% to fluorophenyl methanol transformation efficiency, and the yield of p-Fluorobenzenecarboxaldehyde is 94.5%.
embodiment 3
(1) device: with reference to the mode of connection of Fig. 2 determination tubular reactor, conduit types is: (3a+3c) once-through type passage+oblique side's cake formula pulse diameter varied narrow rectangular tube road, duct length is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil or water.
(2) adjacent for substrate chlorobenzyl alcohol, stirring solvent are mixed, the mixed solution of catalyzer and clorox is adjusted to required pH value, input in head tank 1,2 respectively.Then two strands of materials pump in tubular reactor by volume pump 3,4, first through preheating zone 5,6 preheating and then enter reaction zone and carry out hybrid reaction.The preheating temperature of reactive system and temperature of reaction are set as 25 DEG C.Wherein, 2,2, the TEMPO catalyzer of 6,6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) or support, the mol ratio of its consumption and adjacent chlorobenzyl alcohol is 0.01: 1, the volume ratio of adjacent chlorobenzyl alcohol and organic solvent acetonitrile is 1: 15, and chlorine bleach liquor's pH value is 9 concentration is 1.2mol/L.By regulating the mol ratio of the adjacent chlorobenzyl alcohol of the flow rate control of volume pump and clorox to be 1: 1.3, reaction time is 60s.React after product and entered holding tank from reactor outlet continuous discharge, added Sulfothiorine and carry out cancellation.Analyze through GC, the adjacent chlorobenzyl alcohol transformation efficiency of raw material is 98.4%, and the yield of o-chlorobenzaldehyde is 95.3%.
embodiment 4
(1) device: with reference to the mode of connection of Fig. 2 determination tubular reactor, conduit types is: the HeartCell structure of (3a+3e) once-through type passage+Corning, duct length is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil or water.
(2) substrate meta-methoxy phenylcarbinol, stirring solvent are mixed, the mixed solution of catalyzer and clorox is adjusted to required pH value, input in head tank 1,2 respectively.Then two strands of materials pump in tubular reactor by volume pump 3,4, first through preheating zone 5,6 preheating and then enter reaction zone and carry out hybrid reaction.The preheating temperature of reactive system and temperature of reaction are set as 15 DEG C.Wherein, 2,2,6, the TEMPO catalyzer of 6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) or support, the mol ratio of its consumption and meta-methoxy phenylcarbinol is 0.015: 1, and the volume ratio of meta-methoxy phenylcarbinol and organic solvent acetonitrile is 1: 10, and chlorine bleach liquor's pH value is 8 concentration is 1.1mol/L.By regulating the flow rate control meta-methoxy phenylcarbinol of volume pump and the mol ratio of clorox to be 1: 1.15, reaction time is 90s.React after product and entered holding tank from reactor outlet continuous discharge, added Sulfothiorine and carry out cancellation.Analyze through GC, raw material meta-methoxy phenylcarbinol transformation efficiency is 99.1%, and the yield of NSC 43794 is 96.2%.
embodiment 5
(1) device: with reference to the mode of connection of Fig. 2 determination tubular reactor, conduit types is: (3a+3d) once-through type passage+enhancing mixed type cake formula narrow rectangular tube road, duct length is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil or water.
(2) substrate 4-bromobenzene methyl alcohol, stirring solvent are mixed, the mixed solution of catalyzer and clorox is adjusted to required pH value, input in head tank 1,2 respectively.Then two strands of materials pump in tubular reactor by volume pump 3,4, first through preheating zone 5,6 preheating and then enter reaction zone and carry out hybrid reaction.The preheating temperature of reactive system and temperature of reaction are set as 10 DEG C.Wherein, 2,2, the TEMPO catalyzer of 6,6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) or support, the mol ratio of its consumption and 4-bromobenzene methyl alcohol is 0.015: 1,4-bromobenzene methyl alcohol and organic solvent N, N, the volume ratio of-dimethyl formamide is 1: 10, and chlorine bleach liquor's pH value is 7 concentration is 0.9mol/L.By regulating the flow rate control 4-bromobenzene methyl alcohol of volume pump and the mol ratio of clorox to be 1: 1.1, reaction time is 120s.React after product and entered holding tank from reactor outlet continuous discharge, added Sulfothiorine and carry out cancellation.Analyze through GC, raw material 4-bromobenzene methanol conversion is the yield of 97.5%, 4-bromobenzaldehyde is 94.7%.
embodiment 6
(1) device: with reference to the mode of connection of Fig. 2 determination tubular reactor, conduit types is: (3a+3b) once-through type passage+cake formula pulse diameter varied narrow rectangular tube road, duct length is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil or water.
(2) substrate is mixed chlorobenzene methanol, stirring solvent, the mixed solution of catalyzer and clorox is adjusted to required pH value, input in head tank 1,2 respectively.Then two strands of materials pump in tubular reactor by volume pump 3,4, first through preheating zone 5,6 preheating and then enter reaction zone and carry out hybrid reaction.The preheating temperature of reactive system and temperature of reaction are set as 5 DEG C.Wherein, 2,2, the TEMPO catalyzer of 6,6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) or support, its consumption be 0.02: 1 to the mol ratio of chlorobenzene methanol, to chlorobenzene methanol and organic solvent N, N, the volume ratio of-dimethyl formamide is 1: 10, and chlorine bleach liquor's pH value is 8 concentration is 0.8mol/L.By regulating the mol ratio of flow rate control to chlorobenzene methanol and clorox of volume pump to be 1: 1.2, reaction time is 150s.React after product and entered holding tank from reactor outlet continuous discharge, added Sulfothiorine and carry out cancellation.Analyze through GC, raw material is 98.6% to chlorobenzene methanol transformation efficiency, and the yield of 4-chloro-benzaldehyde is 95.4%.
embodiment 7
(1) device: with reference to the mode of connection of Fig. 2 determination tubular reactor, conduit types is: the HeartCell structure of (3a+3e) once-through type passage+Corning, duct length is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil or water.
(2) substrate phenylethyl alcohol, stirring solvent are mixed, the mixed solution of catalyzer and clorox is adjusted to required pH value, input in head tank 1,2 respectively.Then two strands of materials pump in tubular reactor by volume pump 3,4, first through preheating zone 5,6 preheating and then enter reaction zone and carry out hybrid reaction.The preheating temperature of reactive system and temperature of reaction are set as 0 DEG C.Wherein, 2,2,6, the TEMPO catalyzer of 6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) or support, the mol ratio of its consumption and phenylethyl alcohol is 0.015: 1, phenylethyl alcohol and organic solvent N, N, the volume ratio of-N,N-DIMETHYLACETAMIDE is 1: 10, and chlorine bleach liquor's pH value is 7 concentration is 1.0mol/L.By regulating the flow rate control phenylethyl alcohol of volume pump and the mol ratio of clorox to be 1: 1.2, reaction time is 90s.React after product and entered holding tank from reactor outlet continuous discharge, added Sulfothiorine and carry out cancellation.Analyze through GC, benzene feedstock ethanol conversion is 99.8%, and the yield of methyl phenyl ketone is 96.3%.
embodiment 8
(1) device: with reference to the mode of connection of Fig. 2 determination tubular reactor, conduit types is: the HeartCell structure of (3a+3e) once-through type passage+Corning, duct length is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil or water.
(2) substrate 4-fluorobenzene ethanol, stirring solvent are mixed, the mixed solution of catalyzer and clorox is adjusted to required pH value, input in head tank 1,2 respectively.Then two strands of materials pump in tubular reactor by volume pump 3,4, first through preheating zone 5,6 preheating and then enter reaction zone and carry out hybrid reaction.The preheating temperature of reactive system and temperature of reaction are set as 50 DEG C.Wherein, 2,2, the TEMPO catalyzer of 6,6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) or support, the mol ratio of its consumption and 4-fluorobenzene ethanol is 0.02: 1,4-fluorobenzene ethanol and organic solvent N, N, the volume ratio of-N,N-DIMETHYLACETAMIDE is 1: 10, and chlorine bleach liquor's pH value is 8 concentration is 1.5mol/L.By regulating the flow rate control 4-fluorobenzene ethanol of volume pump and the mol ratio of clorox to be 1: 1.3, reaction time is 60s.React after product and entered holding tank from reactor outlet continuous discharge, added Sulfothiorine and carry out cancellation.Analyze through GC, raw material 4-fluorophenethyl alcohol conversion is the yield of 98.7%, 4-fluoro acetophenone is 95.1%.
embodiment 9
(1) device: with reference to the mode of connection of Fig. 2 determination tubular reactor, conduit types is: (3a+3d) once-through type passage+enhancing mixed type cake formula narrow rectangular tube road, duct length is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil or water.
(2) substrate m-nitro ethanol, stirring solvent are mixed, the mixed solution of catalyzer and clorox is adjusted to required pH value, input in head tank 1,2 respectively.Then two strands of materials pump in tubular reactor by volume pump 3,4, first through preheating zone 5,6 preheating and then enter reaction zone and carry out hybrid reaction.The preheating temperature of reactive system and temperature of reaction are set as 25 DEG C.Wherein, 2,2, the TEMPO catalyzer of 6,6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) or support, the mol ratio of its consumption and m-nitro ethanol is 0.01: 1, the volume ratio of m-nitro ethanol and organic solvent acetonitrile is 1: 12, and chlorine bleach liquor's pH value is 6 concentration is 0.6mol/L.By regulating the flow rate control m-nitro ethanol of volume pump and the mol ratio of clorox to be 1: 1.1, reaction time is 150s.React after product and entered holding tank from reactor outlet continuous discharge, added Sulfothiorine and carry out cancellation.Analyze through GC, raw material m-nitro ethanol conversion is 97.4%, and the yield of m-nitroacetophenone is 94.6%.
embodiment 10
(1) device: with reference to the mode of connection of Fig. 2 determination tubular reactor, conduit types is: (3a) PFA pipe passageway, and duct length is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil or water.
(2) substrate 4-chlorophenethylol, stirring solvent are mixed, the mixed solution of catalyzer and clorox is adjusted to required pH value, input in head tank 1,2 respectively.Then two strands of materials pump in tubular reactor by volume pump 3,4, first through preheating zone 5,6 preheating and then enter reaction zone and carry out hybrid reaction.The preheating temperature of reactive system and temperature of reaction are set as 20 DEG C.Wherein, 2,2, the TEMPO catalyzer of 6,6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) or support, the mol ratio of its consumption and 4-chlorophenethylol is 0.025: 1, the volume ratio of 4-chlorophenethylol and organic solvent acetonitrile is 1: 10, and chlorine bleach liquor's pH value is 7 concentration is 0.8mol/L.By regulating the flow rate control 4-chlorophenethylol of volume pump and the mol ratio of clorox to be 1: 1.25, reaction time is 120s.React after product and entered holding tank from reactor outlet continuous discharge, added Sulfothiorine and carry out cancellation.Analyze through GC, raw material 4-chlorophenethylol transformation efficiency is the yield of 97.9%, 4-chloro-acetophenone is 94.8%.
embodiment 11
(1) conduit types is: (3a+3b) once-through type passage+cake formula pulse diameter varied narrow rectangular tube road, duct length is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil or water.
(2) substrate 4-anisole ethanol, stirring solvent are mixed, the mixed solution of catalyzer and clorox is adjusted to required pH value, input in head tank 1,2 respectively.Then two strands of materials pump in tubular reactor by volume pump 3,4, first through preheating zone 5,6 preheating and then enter reaction zone and carry out hybrid reaction.The preheating temperature of reactive system and temperature of reaction are set as 10 DEG C.Wherein, 2,2,6, the TEMPO catalyzer of 6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) or support, the mol ratio of its consumption and 4-anisole ethanol is 0.01: the volume ratio of Isosorbide-5-Nitrae-anisole ethanol and organic solvent acetonitrile is 1: 10, and chlorine bleach liquor's pH value is 9 concentration is 0.5mol/L.By regulating the flow rate control 4-anisole ethanol of volume pump and the mol ratio of clorox to be 1: 1.1, reaction time is 140s.React after product and entered holding tank from reactor outlet continuous discharge, added Sulfothiorine and carry out cancellation.Analyze through GC, raw material 4-anisole ethanol conversion is the yield of 98.7%, 4-methoxyacetophenone is 95.4%.
embodiment 12
(1) device: with reference to the mode of connection of Fig. 2 determination tubular reactor, conduit types is: the HeartCell structure of (3a+3e) once-through type passage+Corning, duct length is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil or water.
(2) substrate 4-methylbenzene ethanol, stirring solvent are mixed, the mixed solution of catalyzer and clorox is adjusted to required pH value, input in head tank 1,2 respectively.Then two strands of materials pump in tubular reactor by volume pump 3,4, first through preheating zone 5,6 preheating and then enter reaction zone and carry out hybrid reaction.The preheating temperature of reactive system and temperature of reaction are set as 0 DEG C.Wherein, 2,2, the TEMPO catalyzer of 6,6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) or support, the mol ratio of its consumption and 4-methylbenzene ethanol is 0.005: 1,4-methylbenzene ethanol and organic solvent N, N, the volume ratio of-N,N-DIMETHYLACETAMIDE is 1: 10, and chlorine bleach liquor's pH value is 8 concentration is 1.2mol/L.By regulating the flow rate control 4-methylbenzene ethanol of volume pump and the mol ratio of clorox to be 1: 1.1, reaction time is 150s.React after product and entered holding tank from reactor outlet continuous discharge, added Sulfothiorine and carry out cancellation.Analyze through GC, raw material 4-methylbenzene ethanol conversion is the yield of 98.9%, 4-methyl acetophenone is 96.7%.
embodiment 13
(1) device: with reference to the mode of connection of Fig. 2 determination tubular reactor, conduit types is: (3a+3d) once-through type passage+enhancing mixed type cake formula narrow rectangular tube road, duct length is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil or water.
(2) substrate 1-phenyl-n-butyl alcohol, stirring solvent are mixed, the mixed solution of catalyzer and clorox is adjusted to required pH value, input in head tank 1,2 respectively.Then two strands of materials pump in tubular reactor by volume pump 3,4, first through preheating zone 5,6 preheating and then enter reaction zone and carry out hybrid reaction.The preheating temperature of reactive system and temperature of reaction are set as 10 DEG C.Wherein, 2,2, the TEMPO catalyzer of 6,6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) or support, the mol ratio of its consumption and 1-phenyl-n-butyl alcohol is 0.015: 1,1-phenyl-n-butyl alcohol and organic solvent N, N, the volume ratio of-dimethyl formamide is 1: 12, and chlorine bleach liquor's pH value is 9 concentration is 0.6mol/L.By regulating the flow rate control 1-phenyl-n-butyl alcohol of volume pump and the mol ratio of clorox to be 1: 1.05, reaction time is 120s.React after product and entered holding tank from reactor outlet continuous discharge, added Sulfothiorine and carry out cancellation.Analyze through GC, raw material 1-phenyl-n-butyl alcohol transformation efficiency is 96.2%, and the yield of phenyl propyl ketone is 90.5%.
embodiment 14
(1) device: with reference to the mode of connection of Fig. 2 determination tubular reactor, conduit types is: the HeartCell structure of (3a+3e) once-through type passage+Corning, duct length is determined according to flow velocity and reaction time, and heat transferring medium is thermal oil or water.
(2) substrate 1-phenyl-1-propanol, stirring solvent mixed and squeeze into respectively in head tank 1,2 after the mixed solution of catalyzer and clorox is regulated required pH value.Then two strands of materials are squeezed in tubular reactor by volume pump 3,4, first through preheating zone 5,6 preheating and then enter reaction zone and carry out hybrid reaction.The preheating temperature of reactive system and temperature of reaction are set as 0 DEG C.Wherein, 2,2, the TEMPO catalyzer of 6,6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) or support, the mol ratio of its consumption and 1-phenyl-1-propanol is 0.01: 1, the volume ratio of 1-phenyl-1-propanol and organic solvent acetonitrile is 1: 10, and chlorine bleach liquor's pH value is 8 concentration is 0.5mol/L.By regulating the flow rate control 1-phenyl-1-propanol of volume pump and the mol ratio of clorox to be 1: 1.1, reaction time is 90s.React after product and entered holding tank from reactor outlet continuous discharge, added Sulfothiorine and carry out cancellation.Analyze through GC, raw material 1-phenyl-1-propanol transformation efficiency is 97.3%, and the yield of phenyl propyl ketone is 93.2%.
Claims (7)
1. adopt tubular reactor that aromatic alcohol continuous oxidation is prepared a method for aromatic aldehyde ketone, it is characterized in that carrying out according to following step:
(1) take aromatic alcohol compound as substrate, hypochlorite is oxygenant, 2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) is catalyzer, nitrogenous type organic is solvent, and in the tubular reactor of different structure, continuous oxidation prepares aromatic aldehyde ketone;
(2) first at room temperature, substrate aromatic alcohol compound and nitrogenous organic solvent are uniformly mixed, then TEMPO and hypochlorite solutions are uniformly mixed and form composite catalytic oxidation agent and be adjusted to required pH value with acid; Two strands of materials are squeezed into continuously through volume pump respectively and after preheating mixing, are entered reaction zone in tubular reactor and react, and temperature of reaction is controlled by outer loop heat-exchange system;
(3) method by regulating flow velocity and meter to weigh controls the mol ratio of reaction mass, is controlled the residence time of mixing of materials reaction by the caliber size and length changing tubular reactor; After completion of the reaction, product flows out from reactor end and enters holding tank, and enter last handling process, product obtains target product after fractionation by distillation purifying.
2. aromatic alcohol continuous oxidation is prepared the method for aromatic aldehyde ketone by a kind of tubular reactor that adopts according to claims 1, it is characterized in that described aromatic alcohol has following structure:
Wherein, R
1be selected from the one in halogen, methoxyl group, nitro, methyl, hydrogen; R
2be selected from the alkyl of C1 ~ C8, hydrogen.
3. aromatic alcohol continuous oxidation is prepared the method for aromatic aldehyde ketone by a kind of tubular reactor that adopts according to claims 1, it is characterized in that described catalyzer is 2,2,6, the TEMPO of 6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) or support, the mol ratio of its consumption and substrate aromatic alcohol compound is in (0.005 ~ 0.03): 1, and wherein preferred molar ratio is (0.005 ~ 0.015): 1.
4. aromatic alcohol continuous oxidation is prepared the method for aromatic aldehyde ketone by a kind of tubular reactor that adopts according to claims 1, it is characterized in that described hypochlorite is clorox, potassium hypochlorite, Losantin, its strength of solution is 0.3 ~ 1.8mol/L, preferred concentration is 0.5 ~ 1.2mol/L, preferable ph scope 6 ~ 9; The preferred molar ratio of hypochlorite and substrate aromatic alcohol compound is (1.0 ~ 1.5): 1.
5. aromatic alcohol continuous oxidation is prepared the method for aromatic aldehyde ketone by a kind of tubular reactor that adopts according to claims 1, it is characterized in that described nitrogenous organic solvent comprises: acetonitrile, N, N ,-dimethyl formamide, N, N ,-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone; Wherein the volume ratio of solvent and aromatic alcohol compound is in (5 ~ 15): 1.
6. aromatic alcohol continuous oxidation is prepared the method for aromatic aldehyde ketone by a kind of tubular reactor that adopts according to claims 1, and it is characterized in that: temperature of reaction is-10 ~ 50 DEG C, preferable reaction temperature is 0 ~ 25 DEG C, and reaction time is 60s ~ 180s.
7. aromatic alcohol continuous oxidation is prepared the method for aromatic aldehyde ketone by a kind of tubular reactor that adopts according to claims 1, it is characterized in that: total overall reaction process is all carried out continuously in the tubular reactor of ad hoc structure, this reactive system comprises the difference in functionality regions such as raw material storage tank, reaction zone, product collection; Channel of reactor structure comprises: pipe once-through type channel architecture, cake formula pulse diameter varied narrow rectangular tube road structure, oblique side's cake formula pulse diameter varied narrow rectangular tube road structure, enhancing mixed type cake formula narrow rectangular tube road structure, cardioid channel architecture.
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