CN103880851B - The continuous production processes of four metal arylide porphyrins - Google Patents
The continuous production processes of four metal arylide porphyrins Download PDFInfo
- Publication number
- CN103880851B CN103880851B CN201410087459.XA CN201410087459A CN103880851B CN 103880851 B CN103880851 B CN 103880851B CN 201410087459 A CN201410087459 A CN 201410087459A CN 103880851 B CN103880851 B CN 103880851B
- Authority
- CN
- China
- Prior art keywords
- tower
- reaction
- constant temperature
- stirring reaction
- porphyrin
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses the continuous production processes of four metal arylide porphyrins, this technique first solvent is joined heterogeneous reaction to be separated in synchronous reaction device, described reactor comprises the stirring reaction tower with reflux, with at least two constant temperature sedimentation towers be communicated with stirring reaction tower bottom; Described stirring reaction Ta Tanei comprises gas phase zone, reaction zone; During reaction, described solvent is full of in reaction zone and constant temperature sedimentation tower, when raised temperature reaches the reflux temperature of solvent, reaction raw materials four aryl porphines and metal-salt are joined in stirring reaction tower and react or react under the condition passing into air, the four metal arylide porphyrins that reaction generates enter constant temperature sedimentation tower from the direct sedimentation in reaction zone under gravity, until when filling four metal arylide porphyrins in constant temperature sedimentation tower, described stirring reaction tower is switched to the constant temperature sedimentation tower filling solvent with another be communicated with, hocket thus, carry out continuous seepage; This technique energy high yield, low cost, continuous prodution high purity four metal arylide porphyrin.
Description
Technical field
The present invention relates to a kind of continuous production processes of four metal arylide porphyrins, belong to catalyzer synthesis field.
Background technology
Metalloporphyrin is widely used as hydrocarbon-air oxide catalyst, also can be used as luminescent material.In laboratory, four aryl divalent metal porphyrin TRPPM(2) generally adopt four aryl porphines TRPPH
2(1) in DMF with metal-salt M
2+metallization preparation:
And four aryl trivalent metal porphyrin TRPPMX(3) generally adopt in the presence of an oxidizer by four aryl porphines TRPPH
2(1) in DMF with metal-salt M
2+metallization preparation:
Four aryl porphines TRPPH
2metallization processes be a reversing process, it is greatly excessive to need metal-salt when preparation four metal arylide porphyrin TRPPM; In addition, four aryl porphines TRPPH
2all bad with the solubility property of four metal arylide porphyrin TRPPM, and the solubility property of product four metal arylide porphyrin TRPPM is than reactant four aryl porphines TRPPH
2poorer.Therefore, the preparation of four metal arylide porphyrins can only be carried out in dilute solution.Although take above-mentioned measure, in four metal arylide Porphyrin Products of synthesis, still can contain a small amount of raw material four aryl porphines, need the four metal arylide porphyrins that just can obtain purification further by chromatographic separation.These characteristics in four metal arylide porphyrin synthesis, the difficulty that in causing industrial mass metalloporphyrin to be produced, product is purified and the process of a large amount of solvent, increase production cost.
Summary of the invention
The object of the invention is to be to provide a kind of with four aryl porphines and metal-salt for raw material, by simple process condition, high yield, low cost, the technique of the highly purified four aryl divalent metal porphyrins of continuous prodution.
Another object of the present invention is to provide one with four aryl porphines, divalent metal salt and air for raw material, by simple process condition, and high yield, low cost, the technique of the highly purified four aryl trivalent metal porphyrins of continuous seepage.
The technique that to the invention provides with four aryl porphines and metal-salt be raw material continuous seepage four metal arylide porphyrin, this technique first solvent is joined heterogeneous reaction to be separated in synchronous reaction device, described heterogeneous reaction separation synchronous reaction device comprises the stirring reaction tower with reflux, at least two constant temperature sedimentation towers be communicated with described stirring reaction tower bottom, described stirring reaction Ta Tanei comprises the gas phase zone on top, the reflux Link Port at the reaction zone of middle and lower part and top and raw material feeding mouth, agitator is provided with in the reaction zone of described stirring reaction tower, during reaction, solvent is full of in described reaction zone and constant temperature sedimentation tower, when raised temperature reaches the reflux temperature of solvent, reaction raw materials four aryl porphines and metal-salt are pressed the mixed in molar ratio of 1:1 ~ 2, add stirring reaction tower in batches or continuously from the raw material feeding mouth of described stirring reaction top of tower to react, when react the concentration proceeding to four metal arylide Porphyrin Products in reaction solution reach capacity solubleness time, four described metal arylide porphyrin crystals are separated out, enter constant temperature sedimentation tower from the direct sedimentation in reaction zone of described stirring reaction tower under gravity simultaneously, liquid now in described constant temperature sedimentation tower is then risen by four metal arylide porphyrin exclusions of sedimentation and enters in described stirring reaction tower, reaction is constantly carried out, until when filling four metal arylide porphyrins in constant temperature sedimentation tower, described stirring reaction tower is switched to the constant temperature sedimentation tower filling solvent with another and is communicated with, and the constant temperature sedimentation tower filling four metal arylide porphyrins is taken off process, hocket thus, carry out continuous seepage, described solvent is benzene,toluene,xylene, CH
2cl
2, CHCl
3, one or more in DMF.
Such scheme is suitable for the reaction not needing to pass into air in raw material reaction process.
The metal-salt being applicable to such scheme in the present invention is a kind of in the acetate of the cobalt of solubility, zinc, copper, nickel, magnesium or vanadium or halogeno salt or acetylacetonate.
Present invention also offers with four aryl porphines, divalent metal salt and the air technique for raw material continuous seepage four metal arylide porphyrin, this technique first solvent is joined heterogeneous reaction to be separated in synchronous reaction device, described heterogeneous reaction separation synchronous reaction device comprises the stirring reaction tower with reflux, at least two constant temperature sedimentation towers be communicated with described stirring reaction tower bottom, described stirring reaction Ta Tanei comprises the gas phase zone on top, the reflux Link Port at the reaction zone of middle and lower part and top and raw material feeding mouth, agitator is provided with in the reaction zone of described stirring reaction tower, during reaction, solvent is full of in described reaction zone and constant temperature sedimentation tower, when raised temperature reaches the reflux temperature of solvent, reaction raw materials four aryl porphines and divalent metal salt are pressed the mixed in molar ratio of 1:1 ~ 2, add continuously or in batches from the raw material feeding mouth of described stirring reaction top of tower, and air passes into continuously from described stirring reaction tower bottom, after gas distributor dispersion, to contact with divalent metal salt with four aryl porphines of described reaction zone and react, when react the concentration proceeding to four metal arylide Porphyrin Products in reaction solution reach capacity solubleness time, four described metal arylide porphyrin crystals are separated out, enter constant temperature sedimentation tower from the direct sedimentation in reaction zone of described stirring reaction tower under gravity simultaneously, reaction solution now in described constant temperature sedimentation tower is then risen by four metal arylide porphyrin exclusions of sedimentation and enters in described stirring reaction tower, reaction is constantly carried out, until when filling four metal arylide porphyrins in constant temperature sedimentation tower, described stirring reaction tower is switched to the constant temperature sedimentation tower filling solvent with another and is communicated with, and the constant temperature sedimentation tower filling four metal arylide porphyrins is taken off process, hocket thus, carry out continuous seepage, described solvent is benzene,toluene,xylene, CH
2cl
2, CHCl
3, one or more in DMF.
Such scheme is suitable for the reaction needing to pass into air in raw material reaction process.
The divalent metal salt that the present invention is applicable to such scheme is divalence acetate or the divalence halogeno salt of iron, manganese or chromium.
It is 1 ~ 5wt% that described reaction raw materials adds to maintain the concentration of four aryl porphines in reaction solution continuously or in batches
Excessive solvent in described stirring reaction tower is from the reflux extraction of stirring reaction top of tower.
The unreacted gas fraction of described reaction enters the gas phase zone on stirring reaction tower top, and the reflux through stirring reaction top of tower is derived emptying.
Four described aryl porphines have formula 1 structure; Divalent metal porphyrin has formula 2 structure; Trivalent metal porphyrin has formula 3 structure;
Wherein,
R is hydrogen atom, alkyl, alkoxyl group, hydroxyl, halogen, amido, amino or nitro;
In divalent metal porphyrin, M is cobalt, zinc, copper, nickel, magnesium or vanadium;
In trivalent metal porphyrin, M is iron, manganese, chromium, cobalt or vanadium.
The described solubleness of four metal arylide Porphyrin Products in reaction solution be obtained by reacting is less than four aryl porphines, when the solubleness of four metal arylide porphyrins in reaction solution reaches capacity, adding of reaction raw materials four aryl porphines makes the further positive dirction of reaction move, separate out four metal arylide porphyrin crystals, and utilize the proportion of four metal arylide porphyrins to be greater than the character of reaction solution and other intermediate products, in time settlement separate go out four metal arylide porphyrin crystals, make reaction continue to move to positive dirction.
The reaction zone of described middle and lower part and the boundary of described gas phase zone are that stirring reaction tower is apart from tower top >=1/3 tower wall At The Height.
In described constant temperature sedimentation tower, four metal arylide Porphyrin Products directly take out, suction filtration, and through hot wash, washing with alcohol, obtains pure four metal arylide porphyrin products.
The water that described reaction generates and solvent form azeotrope by reflux reflux-withdrawal.
Described stirring reaction tower blade diameter length ratio is 1:20 ~ 40; Be preferably 1:25 ~ 35; Most preferably be 1:30.
Described production technique switches constant temperature sedimentation tower by constantly hocketing, and the constant temperature sedimentation tower filling four metal arylide porphyrins is taken off process, realizes continuous prodution.
Described gas-liquid-solid heterogeneous reaction is separated synchronous reaction device and comprises stirring reaction tower, with at least two constant temperature sedimentation towers be communicated with described stirring reaction tower bottom.
Described stirring reaction Ta Tanei comprises the gas phase zone on top, the reaction zone of middle and lower part, the reflux Link Port at top and reaction raw materials feeding mouth; The reaction zone of described middle and lower part and the boundary of described gas phase zone are that stirring reaction tower is apart from tower top >=1/3 tower wall At The Height.
Described stirring reaction tower, when needs pass into gas reaction, can at stirring reaction Ta Tanei lower gas material-guiding inlet and gas distributor.
The Link Port of described stirring reaction tower tower bottom and at least two structures, the constant temperature sedimentation tower that size is identical connect.
Agitator is provided with in the reaction zone of described stirring reaction tower.
Described constant temperature sedimentation tower top is provided with the Link Port be connected with described stirring reaction tower bottom; Constant temperature sedimentation tower top is provided with solvent feeding mouth, and constant temperature sedimentation tower bottom is provided with product discharge mouth; Stirring reaction tower bottom Link Port is connected by the Link Port of threeway with constant temperature sedimentation tower top.
Described constant temperature sedimentation tower top is also provided with manhole and vision slit.
Beneficial effect of the present invention: the present invention utilizes the solubleness of four metal arylide porphyrins relatively little first, and proportion is relative to intermediate product and the large physicochemical characteristic of solvent, be liquid-solid in conjunction with the present invention or the reaction of gas-liquid-solid heterogeneous reaction design be separated the reactor synchronously carried out, can by four aryl porphines and reacting metal salt or while generating four metal arylide porphyrins by atmospheric oxidation, synchronously the four metal arylide Porphyrin Products generated are separated from oxidizing reaction system, thus achieve the high yield of high purity four metal arylide porphyrin, highly selective continuous prodution, greatly reduce the production cost of four metal arylide porphyrins.Heterogeneous reaction of the present invention is separated synchronous reaction device and the four metal arylide Porphyrin Products generated can be separated in time, breaking chemical equilibrium makes reaction move to positive dirction, reaction is carried out continuously, product is at the reaction temperatures with Precipitation on the one hand, effectively prevent technique four aryl porphines raw materials and four metal arylide Porphyrin Products eutectoid in cooling crystallization process in the past, effectively improve product purity, and, in this technique, metal-salt and four aryl porphines reaction mol ratio are close to 1:1, also solve and rely on excessive more than 10 times of metal salt concentrations that balance positive dirction is moved in the past, cause the metal-salt that there is a large amount of difficult removing in product, make the defect that product purity reduces, simultaneously, in time four metal arylide Porphyrin Products are separated from oxidizing reaction system, the generation of the side reactions such as the high temperature demetalization of the four metal arylide Porphyrin Products avoided, effective raising productive rate, on the other hand, produce and carry out continuously, effectively prevent a large amount of use of solvent and the recycling process of solvent in technique in the past, make process simplification, energy consumption reduces, and greatly reduces production cost.The reflux that the present invention is arranged, and the water that energy extraction excessive solvent and reaction generate, can emptying unreacted gas fraction when having gas to participate in reaction, the solvent refluxing of entrained air is reclaimed simultaneously, not only ensure that the balance of reaction system, reaction can be made to carry out continuously, reduce energy consumption, decrease environmental pollution.To sum up advantage, technique energy serialization high yield of the present invention, four metal arylide porphyrins of low cost synthesis of high purity, productive rate reaches more than 99%, and in product, four metal arylide porphyrin purity reach more than 99%.
Accompanying drawing explanation
[Fig. 1] is liquid-solid heterogeneous reaction separation synchronous reaction device of the present invention;
[Fig. 2] is gas-liquid-solid heterogeneous reaction separation synchronous reaction device of the present invention;
A is constant temperature sedimentation tower 11 top interface schema;
B is the top interface schema of stirring reaction tower 1;
C is reflux;
Figure number illustrates: 1 is stirring reaction tower, and 2 is reflux interface, and 3 is gas raw material introducing port, 4 is gas distributor, and 5 is manhole, 6 solvent feeding mouths, 7 is reaction raw materials feeding mouth, and 8 is product discharge mouth, and 9 is vision slit, 10 is Y-tube, and 11 be constant temperature sedimentation tower I, 12 is constant temperature sedimentation tower II, 13 is agitator, and 14 is heating jacket, and 15 is spherical condensation tube, 16 is water trap, and 17,18 is Link Port.
Embodiment
Following examples are intended to further illustrate content of the present invention, instead of limit the scope of the invention.
Embodiment 1
Adopt the liquid-solid heterogeneous reaction shown in Fig. 1 to be separated synchronous reaction device, prepare four pairs of propyl group phenyl Cobalt Porphyrin products with four pairs of propyl group phenyl porphine and Cobaltous diacetate for raw material carries out atmospheric oxidation; Wherein, stirring reaction tower blade diameter length ratio is 1:20; Be provided with the constant temperature sedimentation tower that constant temperature sedimentation tower I and constant temperature sedimentation tower II two sizes are identical, structure is consistent; Reaction solution export mouth is from reaction tower top 4/9 place tower body At The Height.
Stirring reaction tower is communicated with constant temperature sedimentation tower I by the threeway controlled under stirring reaction tower, toluene is joined heterogeneous reaction from the solvent feeding mouth at constant temperature sedimentation tower top to be separated synchronous reaction device, until in the reaction zone being full of stirring reaction tower and constant temperature sedimentation tower I, when raised temperature reaches refluxing toluene temperature, four pairs of propyl group phenyl porphine and Cobaltous diacetate are pressed the mixed in molar ratio of 1:1, add continuously from the raw material feeding mouth of stirring reaction top of tower, maintaining the concentration of four pairs of propyl group phenyl porphine in reaction solution is that 1wt% reacts, when react the concentration proceeding to four pairs of propyl group phenyl Cobalt Porphyrin products in reaction solution reach capacity solubleness time, four pairs of propyl group phenyl Cobalt Porphyrin crystal are separated out, four pairs of propyl group phenyl Cobalt Porphyrin enter constant temperature sedimentation tower I from the direct sedimentation in the reaction zone of stirring reaction tower under gravity simultaneously, reaction solution now in described constant temperature sedimentation tower I is then entered in stirring reaction tower by four pairs of propyl group phenyl Cobalt Porphyrin exclusion risings of sedimentation, constantly carrying out of reaction, until when filling four pairs of propyl group phenyl Cobalt Porphyrin in constant temperature sedimentation tower I, control stirring reaction tower to switch to be communicated with the constant temperature sedimentation tower II filling toluene by threeway, and constant temperature sedimentation tower I is taken off, pair propyl group phenyl Cobalt Porphyrin of four wherein directly taken out, suction filtration, through hot wash, washing with alcohol, obtains pure four pairs of propyl group phenyl Cobalt Porphyrin products, hocket thus, carry out continuous seepage.When after stable reaction, every sampling in 4 hours, the purity of four pairs of propyl group phenyl Cobalt Porphyrin products is detected, and the four pairs of propyl group phenyl porphine raw materials entering reaction system and the amount and reaction solution composition obtaining four pairs of propyl group phenyl Cobalt Porphyrin products are detected, calculate productive rate and the purity of four pairs of propyl group phenyl Cobalt Porphyrin, result is as table 1.
The relation of table 1 reaction times and four pairs of propyl group phenyl Cobalt Porphyrin products collection efficiencies and purity
Embodiment 2
Adopt the liquid-solid heterogeneous reaction shown in Fig. 1 to be separated synchronous reaction device, prepare four p-methoxyphenyl zinc porphyrin products with four p-methoxyphenyl porphines and zinc acetate for raw material carries out atmospheric oxidation; Wherein, stirring reaction tower blade diameter length ratio is 1:20; Be provided with the constant temperature sedimentation tower that constant temperature sedimentation tower I and constant temperature sedimentation tower II two sizes are identical, structure is consistent; Reaction solution export mouth is from reaction tower top 4/9 place tower body At The Height.
Stirring reaction tower is communicated with constant temperature sedimentation tower I by the threeway controlled under stirring reaction tower, dimethylbenzene is joined heterogeneous reaction from the solvent feeding mouth at constant temperature sedimentation tower top to be separated synchronous reaction device, until in the reaction zone being full of stirring reaction tower and constant temperature sedimentation tower I, when raised temperature reaches refluxing xylene temperature, four p-methoxyphenyl porphines and zinc acetate are pressed the mixed in molar ratio of 1:1.2, add continuously from the raw material feeding mouth of stirring reaction top of tower, maintaining the concentration of four p-methoxyphenyl porphines in reaction solution is that 1.5wt% reacts, when react the concentration proceeding to four p-methoxyphenyl zinc porphyrin products in reaction solution reach capacity solubleness time, four p-methoxyphenyl zinc porphyrin crystal are separated out, four p-methoxyphenyl zinc porphyrins enter constant temperature sedimentation tower I from the direct sedimentation in the reaction zone of stirring reaction tower under gravity simultaneously, reaction solution now in described constant temperature sedimentation tower I is then entered in stirring reaction tower by four p-methoxyphenyl zinc porphyrin exclusion risings of sedimentation, constantly carrying out of reaction, until when filling four p-methoxyphenyl zinc porphyrins in constant temperature sedimentation tower I, control stirring reaction tower to switch to be communicated with the constant temperature sedimentation tower II filling dimethylbenzene by threeway, and constant temperature sedimentation tower I is taken off, directly taken out by four p-methoxyphenyl zinc porphyrins wherein, suction filtration, through hot wash, washing with alcohol, obtains pure four p-methoxyphenyl zinc porphyrin products, hocket thus, carry out continuous seepage.When after stable reaction, every sampling in 4 hours, the purity of four p-methoxyphenyl zinc porphyrin products is detected, and the four p-methoxyphenyl porphines raw materials entering reaction system and the amount and reaction solution composition obtaining four p-methoxyphenyl zinc porphyrin products are detected, calculate productive rate and the purity of four p-methoxyphenyl zinc porphyrins, result is as table 2.
The relation of table 2 reaction times and four p-methoxyphenyl zinc porphyrin products collection efficiencies and purity
Embodiment 3
Adopt the liquid-solid heterogeneous reaction shown in Fig. 1 to be separated synchronous reaction device, prepare four rubigan Porphyrin Nickel products with four rubigan porphines and acetylacetonate nickel for raw material carries out atmospheric oxidation; Wherein, stirring reaction tower blade diameter length ratio is 1:25; Be provided with the constant temperature sedimentation tower that constant temperature sedimentation tower I and constant temperature sedimentation tower II two sizes are identical, structure is consistent; Reaction solution export mouth is from reaction tower top 2/5 place tower body At The Height.
Stirring reaction tower is communicated with constant temperature sedimentation tower I by the threeway controlled under stirring reaction tower, DMF is joined heterogeneous reaction from the solvent feeding mouth at constant temperature sedimentation tower top to be separated synchronous reaction device, until in the reaction zone being full of stirring reaction tower and constant temperature sedimentation tower I, when raised temperature reaches DMF reflux temperature, four rubigan porphines and acetylacetonate nickel are pressed the mixed in molar ratio of 1:1.4, add continuously from the raw material feeding mouth of stirring reaction top of tower, maintaining the concentration of four rubigan porphines in reaction solution is that 2wt% reacts, when react the concentration proceeding to four rubigan Porphyrin Nickel products in reaction solution reach capacity solubleness time, four rubigan Porphyrin Nickel crystal are separated out, four rubigan Porphyrin Nickels enter constant temperature sedimentation tower I from the direct sedimentation in the reaction zone of stirring reaction tower under gravity simultaneously, reaction solution now in described constant temperature sedimentation tower I is then entered in stirring reaction tower by four rubigan Porphyrin Nickel exclusion risings of sedimentation, constantly carrying out of reaction, until when filling four rubigan Porphyrin Nickels in constant temperature sedimentation tower I, control stirring reaction tower to switch to be communicated with the constant temperature sedimentation tower II filling DMF by threeway, and constant temperature sedimentation tower I is taken off, directly taken out by four rubigan Porphyrin Nickels wherein, suction filtration, through hot wash, washing with alcohol, obtains pure four rubigan Porphyrin Nickel products, hocket thus, carry out continuous seepage.When after stable reaction, every sampling in 4 hours, the purity of four rubigan Porphyrin Nickel products is detected, and the four rubigan porphines raw materials entering reaction system and the amount and reaction solution composition obtaining four rubigan Porphyrin Nickel products are detected, calculate productive rate and the purity of four rubigan Porphyrin Nickels, result is as table 3.
The relation of table 3 reaction times and four rubigan Porphyrin Nickel products collection efficiencies and purity
Embodiment 4
Adopt the liquid-solid heterogeneous reaction shown in Fig. 1 to be separated synchronous reaction device, prepare four m-nitro base porphyrin vanadium products with four m-nitro base porphines and vanadium acetylacetonate for raw material carries out atmospheric oxidation; Wherein, stirring reaction tower blade diameter length ratio is 1:35; Be provided with the constant temperature sedimentation tower that constant temperature sedimentation tower I and constant temperature sedimentation tower II two sizes are identical, structure is consistent; Reaction solution export mouth is from reaction tower top 1/3 place tower body At The Height.
Stirring reaction tower is communicated with constant temperature sedimentation tower I by the threeway controlled under stirring reaction tower, methylene dichloride is joined heterogeneous reaction from the solvent feeding mouth at constant temperature sedimentation tower top to be separated synchronous reaction device, until in the reaction zone being full of stirring reaction tower and constant temperature sedimentation tower I, when raised temperature reaches methylene chloride reflux temperature, four m-nitro base porphines and vanadium acetylacetonate are pressed the mixed in molar ratio of 1:1.6, add continuously from the raw material feeding mouth of stirring reaction top of tower, maintaining the concentration of four m-nitro base porphines in reaction solution is that 2.5wt% reacts, when react the concentration proceeding to four m-nitro base porphyrin vanadium products in reaction solution reach capacity solubleness time, four m-nitro base porphyrin vanadium crystal are separated out, four m-nitro base porphyrin vanadium enter constant temperature sedimentation tower I from the direct sedimentation in the reaction zone of stirring reaction tower under gravity simultaneously, reaction solution now in described constant temperature sedimentation tower I is then entered in stirring reaction tower by four m-nitro base porphyrin vanadium exclusion risings of sedimentation, constantly carrying out of reaction, until when filling four m-nitro base porphyrin vanadium in constant temperature sedimentation tower I, control stirring reaction tower to switch to be communicated with the constant temperature sedimentation tower II filling methylene dichloride by threeway, and constant temperature sedimentation tower I is taken off, directly taken out by four m-nitro base porphyrin vanadium wherein, suction filtration, through hot wash, washing with alcohol, obtains pure four m-nitro base porphyrin vanadium products, hocket thus, carry out continuous seepage.When after stable reaction, every sampling in 4 hours, the purity of four m-nitro base porphyrin vanadium products is detected, and the four m-nitro base porphines raw materials entering reaction system and the amount and reaction solution composition obtaining four m-nitro base porphyrin vanadium products are detected, calculate productive rate and the purity of four m-nitro base porphyrin vanadium, result is as table 4.
The relation of table 4 reaction times and four m-nitro base porphyrin vanadium products collection efficiencies and purity
Embodiment 5
Adopt the liquid-solid heterogeneous reaction shown in Fig. 1 to be separated synchronous reaction device, prepare tetraphenylporphyrin magnesium products with tetraphenylporphines and magnesium chloride for raw material carries out atmospheric oxidation; Wherein, stirring reaction tower blade diameter length ratio is 1:40; Be provided with the constant temperature sedimentation tower that constant temperature sedimentation tower I and constant temperature sedimentation tower II two sizes are identical, structure is consistent; Reaction solution export mouth is from reaction tower top 1/3 place tower body At The Height.
Stirring reaction tower is communicated with constant temperature sedimentation tower I by the threeway controlled under stirring reaction tower, methylene dichloride is joined heterogeneous reaction from the solvent feeding mouth at constant temperature sedimentation tower top to be separated synchronous reaction device, until in the reaction zone being full of stirring reaction tower and constant temperature sedimentation tower I, when raised temperature reaches methylene chloride reflux temperature, tetraphenylporphines and magnesium chloride are pressed the mixed in molar ratio of 1:1.8, add continuously from the raw material feeding mouth of stirring reaction top of tower, maintaining the concentration of tetraphenylporphines in reaction solution is that 3wt% reacts, when react the concentration proceeding to tetraphenylporphyrin magnesium product in reaction solution reach capacity solubleness time, tetraphenylporphyrin magnesium crystal is separated out, tetraphenylporphyrin magnesium enters constant temperature sedimentation tower I from the direct sedimentation in the reaction zone of stirring reaction tower under gravity simultaneously, reaction solution now in described constant temperature sedimentation tower I is then entered in stirring reaction tower by the tetraphenylporphyrin magnesium of sedimentation exclusion rising, constantly carrying out of reaction, until when filling tetraphenylporphyrin magnesium in constant temperature sedimentation tower I, control stirring reaction tower to switch to be communicated with the constant temperature sedimentation tower II filling methylene dichloride by threeway, and constant temperature sedimentation tower I is taken off, directly taken out by tetraphenylporphyrin magnesium wherein, suction filtration, through hot wash, washing with alcohol, obtains pure tetraphenylporphyrin magnesium products, hocket thus, carry out continuous seepage.When after stable reaction, every sampling in 4 hours, the purity of tetraphenylporphyrin magnesium product is detected, and the tetraphenylporphines raw material entering reaction system and the amount and reaction solution composition obtaining tetraphenylporphyrin magnesium product are detected, calculate productive rate and the purity of tetraphenylporphyrin magnesium, result is as table 5.
The relation of table 5 reaction times and tetraphenylporphyrin magnesium products collection efficiency and purity
| Reaction times (h) | The productive rate (%) of tetraphenylporphyrin magnesium | Tetraphenylporphyrin Mg content (%) |
| 4 | 99.1 | 99.1 |
| 8 | 99.2 | 99.2 |
| 12 | 99.2 | 99.3 |
| 16 | 99.2 | 99.3 |
Embodiment 6
Adopting gas-liquid-solid heterogeneous reaction shown in Fig. 2 to be separated synchronous reaction device, is that raw material carries out atmospheric oxidation and prepares four to (N, N '-dimethyl) aminocarbonyl phenyl Manganese Porphyrin product with four to (N, N '-dimethyl) aminocarbonyl phenyl porphines and manganese acetate; Wherein, stirring reaction tower blade diameter length ratio is 1:30; Be provided with the constant temperature sedimentation tower that constant temperature sedimentation tower I and constant temperature sedimentation tower II two sizes are identical, structure is consistent; Reaction solution export mouth is from reaction tower top 1/3 place tower body At The Height.
Stirring reaction tower is communicated with constant temperature sedimentation tower I by the threeway controlled under stirring reaction tower, methylene dichloride is joined heterogeneous reaction from the solvent feeding mouth at constant temperature sedimentation tower top to be separated synchronous reaction device, until in the reaction zone being full of stirring reaction tower and constant temperature sedimentation tower I, when raised temperature reaches methylene chloride reflux temperature, by four to (N, N '-dimethyl) aminocarbonyl phenyl porphines and manganese acetate press the mixed in molar ratio of 1:2, add continuously from the raw material feeding mouth of stirring reaction top of tower, maintain four to (N, N '-dimethyl) concentration of aminocarbonyl phenyl porphines in reaction solution is 3.5wt%, and air passes into continuously from the gas raw material introducing port of stirring reaction tower bottom, after gas distributor dispersion, with four couples (N of reaction zone, N '-dimethyl) aminocarbonyl phenyl porphines contacts with manganese acetate and reacts, when reaction to proceed in reaction solution four to (N, N '-dimethyl) concentration of aminocarbonyl phenyl Manganese Porphyrin product reach capacity solubleness time, four to (N, N '-dimethyl) precipitation of aminocarbonyl phenyl Manganese Porphyrin crystal, four to (N simultaneously, N '-dimethyl) aminocarbonyl phenyl Manganese Porphyrin enters constant temperature sedimentation tower I from the direct sedimentation in the reaction zone of stirring reaction tower under gravity, reaction solution now in described constant temperature sedimentation tower I is then by four couple of sedimentation (N, N '-dimethyl) aminocarbonyl phenyl Manganese Porphyrin exclusion rising enter in stirring reaction tower, constantly carrying out of reaction, until fill in constant temperature sedimentation tower I four to (N, N '-dimethyl) aminocarbonyl phenyl Manganese Porphyrin time, control stirring reaction tower to switch to be communicated with the constant temperature sedimentation tower II filling methylene dichloride by threeway, and constant temperature sedimentation tower I is taken off, four couple wherein (N, N '-dimethyl) aminocarbonyl phenyl Manganese Porphyrin is directly taken out, suction filtration, through hot wash, washing with alcohol, obtains pure four to (N, N '-dimethyl) aminocarbonyl phenyl Manganese Porphyrin product, hocket thus, carry out continuous seepage.When after stable reaction, sampled to four to (N every 4 hours, N '-dimethyl) purity of aminocarbonyl phenyl Manganese Porphyrin product detects, and to entering four couples (N of reaction system, N '-dimethyl) phenyl porphine raw material and obtain four amount of (N, N '-dimethyl) aminocarbonyl phenyl Manganese Porphyrin product and reaction solution composition are detected, calculate four to (N, N '-dimethyl) productive rate of aminocarbonyl phenyl Manganese Porphyrin and purity, result is as table 6.
The relation of table 6 reaction times and four to (N, N '-dimethyl) aminocarbonyl phenyl Manganese Porphyrin products collection efficiency and purity
Embodiment 7
Adopt the gas-liquid-solid heterogeneous reaction shown in Fig. 2 to be separated synchronous reaction device, prepare four pairs of butyl phenyl porphyrin chromium products with four pairs of butyl phenyl porphines and chromium acetate for raw material carries out atmospheric oxidation; Wherein, stirring reaction tower blade diameter length ratio is 1:30; Be provided with the constant temperature sedimentation tower that constant temperature sedimentation tower I and constant temperature sedimentation tower II two sizes are identical, structure is consistent; Reaction solution export mouth is from reaction tower top 1/3 place tower body At The Height.
Stirring reaction tower is communicated with constant temperature sedimentation tower I by the threeway controlled under stirring reaction tower, toluene is joined heterogeneous reaction from the solvent feeding mouth at constant temperature sedimentation tower top to be separated synchronous reaction device, until in the reaction zone being full of stirring reaction tower and constant temperature sedimentation tower I, when raised temperature reaches refluxing toluene temperature, four pairs of butyl phenyl porphines and chromium acetate are pressed the mixed in molar ratio of 1:1.5, add continuously from the raw material feeding mouth of stirring reaction top of tower, maintaining the concentration of four pairs of butyl phenyl porphines in reaction solution is 4wt%, and air passes into continuously from the gas raw material introducing port of stirring reaction tower bottom, after gas distributor dispersion, to contact with chromium acetate with four pairs of butyl phenyl porphines of reaction zone and react, when react the concentration proceeding to four pairs of butyl phenyl porphyrin chromium products in reaction solution reach capacity solubleness time, four pairs of butyl phenyl porphyrin chromium crystal are separated out, four pairs of butyl phenyl porphyrin chromium enter constant temperature sedimentation tower I from the direct sedimentation in the reaction zone of stirring reaction tower under gravity simultaneously, reaction solution now in described constant temperature sedimentation tower I is then entered in stirring reaction tower by four pairs of butyl phenyl porphyrin chromium exclusion risings of sedimentation, constantly carrying out of reaction, until when filling four pairs of butyl phenyl porphyrin chromium in constant temperature sedimentation tower I, control stirring reaction tower to switch to be communicated with the constant temperature sedimentation tower II filling toluene by threeway, and constant temperature sedimentation tower I is taken off, directly taken out by pair butyl phenyl porphyrin chromium of four wherein, suction filtration, through hot wash, washing with alcohol, obtains pure four pairs of butyl phenyl porphyrin chromium products, hocket thus, carry out continuous seepage.When after stable reaction, every sampling in 4 hours, the purity of four pairs of butyl phenyl porphyrin chromium products is detected, and the four pairs of butyl phenyl porphines raw materials entering reaction system and the amount and reaction solution composition obtaining four pairs of butyl phenyl porphyrin chromium products are detected, calculate productive rate and the purity of four pairs of butyl phenyl porphyrin chromium, result is as table 7.
The relation of table 7 reaction times and four pairs of butyl phenyl porphyrin chromium products collection efficiencies and purity
Embodiment 8
Adopt the gas-liquid-solid heterogeneous reaction shown in Fig. 2 to be separated synchronous reaction device, prepare four pairs of butyl phenyl ferrous porphyrin products with four pairs of butyl phenyl porphines and iron protochloride for raw material carries out atmospheric oxidation; Wherein, stirring reaction tower blade diameter length ratio is 1:25; Be provided with the constant temperature sedimentation tower that constant temperature sedimentation tower I and constant temperature sedimentation tower II two sizes are identical, structure is consistent; Reaction solution export mouth is from reaction tower top 1/3 place tower body At The Height.
Stirring reaction tower is communicated with constant temperature sedimentation tower I by the threeway controlled under stirring reaction tower, toluene is joined heterogeneous reaction from the solvent feeding mouth at constant temperature sedimentation tower top to be separated synchronous reaction device, until in the reaction zone being full of stirring reaction tower and constant temperature sedimentation tower I, when raised temperature reaches refluxing toluene temperature, four pairs of butyl phenyl porphines and iron protochloride are pressed the mixed in molar ratio of 1:1.2, add continuously from the raw material feeding mouth of stirring reaction top of tower, maintaining the concentration of four pairs of butyl phenyl porphines in reaction solution is 5wt%, and air passes into continuously from the gas raw material introducing port of stirring reaction tower bottom, after gas distributor dispersion, to contact with iron protochloride with four pairs of butyl phenyl porphines of reaction zone and react, when react the concentration proceeding to four pairs of butyl phenyl ferrous porphyrin products in reaction solution reach capacity solubleness time, four pairs of butyl phenyl ferrous porphyrin crystal are separated out, four pairs of butyl phenyl ferrous porphyrin enter constant temperature sedimentation tower I from the direct sedimentation in the reaction zone of stirring reaction tower under gravity simultaneously, reaction solution now in described constant temperature sedimentation tower I is then entered in stirring reaction tower by four pairs of butyl phenyl ferrous porphyrin exclusion risings of sedimentation, constantly carrying out of reaction, until when filling four pairs of butyl phenyl ferrous porphyrin in constant temperature sedimentation tower I, control stirring reaction tower to switch to be communicated with the constant temperature sedimentation tower II filling toluene by threeway, and constant temperature sedimentation tower I is taken off, pair butyl phenyl ferrous porphyrin of four wherein directly taken out, suction filtration, through hot wash, washing with alcohol, obtains pure four pairs of butyl phenyl ferrous porphyrin products, hocket thus, carry out continuous seepage.When after stable reaction, every sampling in 4 hours, the purity of four pairs of butyl phenyl ferrous porphyrin products is detected, and the four pairs of butyl phenyl porphines raw materials entering reaction system and the amount and reaction solution composition obtaining four pairs of butyl phenyl ferrous porphyrin products are detected, calculate productive rate and the purity of four pairs of butyl phenyl ferrous porphyrin, result is as table 8.
The relation of table 8 reaction times and four pairs of butyl phenyl ferrous porphyrin products collection efficiencies and purity
Claims (7)
1. the continuous production processes of four metal arylide porphyrins, it is characterized in that, first solvent being joined heterogeneous reaction is separated in synchronous reaction device, described heterogeneous reaction separation synchronous reaction device comprises the stirring reaction tower with reflux, at least two constant temperature sedimentation towers be communicated with described stirring reaction tower bottom, described stirring reaction tower comprises the gas phase zone of tower internal upper part, the reflux Link Port at the reaction zone of middle and lower part and top and raw material feeding mouth, agitator is provided with in the reaction zone of described stirring reaction tower, during reaction, solvent is full of in described reaction zone and constant temperature sedimentation tower, when raised temperature reaches the reflux temperature of solvent, reaction raw materials four aryl porphines and metal-salt are pressed the mixed in molar ratio of 1:1 ~ 2, add stirring reaction tower continuously or in batches from the raw material feeding mouth of described stirring reaction top of tower to react, when react the concentration proceeding to four metal arylide Porphyrin Products in reaction solution reach capacity solubleness time, four described metal arylide porphyrin crystals are separated out, enter constant temperature sedimentation tower from the direct sedimentation in reaction zone of described stirring reaction tower under gravity simultaneously, liquid now in described constant temperature sedimentation tower is then risen by four metal arylide porphyrin exclusions of sedimentation and enters in described stirring reaction tower, reaction is constantly carried out, until when filling four metal arylide porphyrins in constant temperature sedimentation tower, described stirring reaction tower is switched to the constant temperature sedimentation tower filling solvent with another and is communicated with, and the constant temperature sedimentation tower filling four metal arylide porphyrins is taken off process, hocket thus, carry out continuous prodution, described solvent is benzene,toluene,xylene, CH
2cl
2, CHCl
3, one or more in DMF,
Described metal-salt is a kind of in the acetate of the cobalt of solubility, zinc, copper, nickel, magnesium or vanadium or halogeno salt or acetylacetonate;
Four described aryl porphines have formula 1 structure:
Four described metal arylide porphyrins have formula 2 structure:
Wherein,
R is hydrogen atom, alkyl, alkoxyl group, hydroxyl, halogen, amido, amino or nitro;
M is cobalt, zinc, copper, nickel, magnesium or vanadium.
2. technique as claimed in claim 1, it is characterized in that, it is 1 ~ 5wt% that described reaction raw materials adds to maintain the concentration of four aryl porphines in reaction solution continuously or in batches.
3. technique as claimed in claim 1, it is characterized in that, the excessive solvent in described stirring reaction tower is from the reflux extraction of stirring reaction top of tower.
4. the continuous production processes of four metal arylide porphyrins, it is characterized in that, first solvent being joined heterogeneous reaction is separated in synchronous reaction device, described heterogeneous reaction separation synchronous reaction device comprises the stirring reaction tower with reflux, at least two constant temperature sedimentation towers be communicated with described stirring reaction tower bottom, described stirring reaction tower comprises the gas phase zone of tower internal upper part, the reflux Link Port at the reaction zone of middle and lower part and top and raw material feeding mouth, agitator is provided with in the reaction zone of described stirring reaction tower, during reaction, solvent is full of in described reaction zone and constant temperature sedimentation tower, when raised temperature reaches the reflux temperature of solvent, reaction raw materials four aryl porphines and divalent metal salt are pressed the mixed in molar ratio of 1:1 ~ 2, add continuously or in batches from the raw material feeding mouth of described stirring reaction top of tower, and air passes into continuously from described stirring reaction tower bottom, after gas distributor dispersion, to contact with divalent metal salt with four aryl porphines of described reaction zone and react, when react the concentration proceeding to four metal arylide Porphyrin Products in reaction solution reach capacity solubleness time, four described metal arylide porphyrin crystals are separated out, enter constant temperature sedimentation tower from the direct sedimentation in reaction zone of described stirring reaction tower under gravity simultaneously, liquid now in described constant temperature sedimentation tower is then risen by four metal arylide porphyrin exclusions of sedimentation and enters in described stirring reaction tower, reaction is constantly carried out, until when filling four metal arylide porphyrins in constant temperature sedimentation tower, described stirring reaction tower is switched to the constant temperature sedimentation tower filling solvent with another and is communicated with, and the constant temperature sedimentation tower filling four metal arylide porphyrins is taken off process, hocket thus, carry out continuous prodution, described solvent is benzene,toluene,xylene, CH
2cl
2, CHCl
3, one or more in DMF, described divalent metal salt is divalence acetate or the divalence halogeno salt of cobalt, iron, manganese, chromium or vanadium, four described aryl porphines have formula 1 structure:
Four described metal arylide porphyrins have formula 3 structure:
Wherein,
R is hydrogen atom, alkyl, alkoxyl group, hydroxyl, halogen, amido, amino or nitro;
X is acetate or halogen;
M is cobalt, iron, manganese, chromium or vanadium.
5. technique as claimed in claim 4, it is characterized in that, it is 1 ~ 5wt% that described reaction raw materials adds to maintain the concentration of four aryl porphines in reaction solution continuously or in batches.
6. technique as claimed in claim 4, it is characterized in that, the excessive solvent in described stirring reaction tower is from the reflux extraction of stirring reaction top of tower.
7. technique as claimed in claim 4, it is characterized in that, the unreacted gas fraction of described reaction enters the gas phase zone on stirring reaction tower top, and the reflux through stirring reaction top of tower is derived emptying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410087459.XA CN103880851B (en) | 2014-03-11 | 2014-03-11 | The continuous production processes of four metal arylide porphyrins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410087459.XA CN103880851B (en) | 2014-03-11 | 2014-03-11 | The continuous production processes of four metal arylide porphyrins |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103880851A CN103880851A (en) | 2014-06-25 |
| CN103880851B true CN103880851B (en) | 2016-03-02 |
Family
ID=50950016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410087459.XA Active CN103880851B (en) | 2014-03-11 | 2014-03-11 | The continuous production processes of four metal arylide porphyrins |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103880851B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646506B (en) * | 2016-01-15 | 2018-04-24 | 唐江涛 | A kind of continuous preparation method of tetraphenyl divalence monometallic porphyrin |
| CN105646507B (en) * | 2016-01-15 | 2018-04-24 | 唐江涛 | A kind of continuous preparation method of tetraphenyl trivalent monometallic porphyrin |
| CN106905333B (en) * | 2017-04-19 | 2019-03-01 | 沅江华龙催化科技有限公司 | A kind of synthetic method of Porphyrin and its derivative |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2686592A (en) * | 1991-10-04 | 1993-05-03 | Sandoz Ltd. | Tetraphenylporphyn derivatives |
| CN1238355C (en) * | 2003-11-21 | 2006-01-25 | 湖南大学 | Metalloporphyrin synthesizing method |
| JP2008255011A (en) * | 2007-03-30 | 2008-10-23 | Tokyo Metropolitan Univ | Amphiphilic metalloporphyrin complex and pharmaceutical composition using the same |
| WO2010028780A2 (en) * | 2008-09-09 | 2010-03-18 | Universität Zürich | Preparation and uses of guanidinium-modified porphyrins and phthalocyanines |
| CN102382116B (en) * | 2011-08-31 | 2013-10-16 | 沅江华龙催化科技有限公司 | Synthesis technology and equipment of tetraaryl cobalt porphyrin |
| CN102408430B (en) * | 2011-09-07 | 2013-11-06 | 沅江华龙催化科技有限公司 | Synthetic process and special equipment for substituted bis [tetraphenylporphinatoiron] |
-
2014
- 2014-03-11 CN CN201410087459.XA patent/CN103880851B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103880851A (en) | 2014-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103755543B (en) | The air oxidation of cyclohexane that utilizes being separated synchronous reaction device based on gas-liquid-solid heterogeneous reaction produces the method for hexanodioic acid | |
| CN103755544B (en) | Method for producing KA oil and adipic acid through oxidizing cyclohexane with air on basis of gas-liquid-solid heterogeneous reaction separation synchronization reactor | |
| CN103880851B (en) | The continuous production processes of four metal arylide porphyrins | |
| CN103755521B (en) | Method for producing KA oil through oxidizing cyclohexane by using air on basis of gas-liquid-solid heterogeneous reaction separation synchronization reactor | |
| CN107573370A (en) | The method that supported copper ion chitosan microball catalysis prepares organoboron compound and β hydroxy compounds | |
| CN104402774B (en) | Method for preparing CLT acid through continuous catalytic hydrogenation reduction | |
| CN107175133A (en) | A kind of silicon dioxide carried copper dipyridyl catalyst and preparation method thereof | |
| CN108003154B (en) | Method for synthesizing paliperidone intermediate by using microchannel reactor | |
| CN103755520B (en) | Method for producing substituted benzyl alcohol, substituted benzaldehyde and substituted benzyl acid through oxidizing substituted methylbenzene with air based on gas-liquid-solid heterogeneous reaction separation synchronization reactor | |
| CN103880852B (en) | The continuous production processes of four aryl porphines | |
| CN103007943A (en) | Catalyst used for preparing ethanol by hydrogenation of acetic ester as well as preparation method and application of catalyst | |
| CN109096318B (en) | Method for preparing organic boron compound and beta-hydroxy compound under catalysis of copper ion-loaded Y-type molecular sieve | |
| CN103819480B (en) | The continuous production processes of four aryl bimetallic porphyrins | |
| CN104844462A (en) | Synthesis process of dimido dipheny compound | |
| CN104387413A (en) | Production method for preparing trialkoxysilane by adopting direct method | |
| CN111744551A (en) | Application of lithium complex in hydroboration reaction of nitrile | |
| CN101619064B (en) | Synthesis and process method for novel polynitrogen heterocycle pharmaceutical intermediates | |
| CN103450306A (en) | Synthetic method of pregnenolone acetate | |
| CN115282913A (en) | Reaction system and method for preparing methyl propionate | |
| CN104496939B (en) | A kind of catalytic hydrogenation prepares the method for piperazine or alkyl piperazine | |
| CN102371180A (en) | Catalyst for use in gas-phase synthesis of diethyl carbonate and preparation method thereof | |
| CN102659757B (en) | Intermediate synthesizing 5-chlorothiophene-3-carbo and preparation method thereof | |
| CN106380490A (en) | One-step synthesis method of (1,5-cyclooctadiene)-dichloro iridium dipolymer | |
| CN102134221A (en) | Solvent-free synthesis of alkyl bridging bis-imidazole salt compound | |
| CN116273185B (en) | Immobilized bifunctional catalyst and method for preparing cyclic carbonate in outer loop reaction process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |