CN112321596A - Method for synthesizing tetraphenylporphyrin by using reflux pipe type reactor - Google Patents
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- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000010992 reflux Methods 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 46
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 40
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 238000006482 condensation reaction Methods 0.000 claims abstract description 3
- 150000008064 anhydrides Chemical class 0.000 claims abstract 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical group CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 23
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- 238000005086 pumping Methods 0.000 claims description 9
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 8
- 235000019260 propionic acid Nutrition 0.000 claims description 8
- 238000004537 pulping Methods 0.000 claims description 8
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 2
- 230000005595 deprotonation Effects 0.000 abstract 1
- 238000010537 deprotonation reaction Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 238000003860 storage Methods 0.000 description 11
- 239000012456 homogeneous solution Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 150000004032 porphyrins Chemical class 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 porphyrin compounds Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 241000219495 Betulaceae Species 0.000 description 1
- KSFOVUSSGSKXFI-GAQDCDSVSA-N CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O Chemical compound CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O KSFOVUSSGSKXFI-GAQDCDSVSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229950003776 protoporphyrin Drugs 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyrrole Compounds (AREA)
Abstract
The invention discloses a method for synthesizing tetraphenylporphyrin by a reflux pipe reactor, which is characterized in that benzaldehyde and pyrrole are subjected to a reaction condensation reaction under the conditions of equimolar ratio and fluidity and the presence of acid or anhydride deprotonation and an oxidant by using the reflux pipe reactor under the conditions of temperature control of 110 ℃ and 140 ℃ and pressure of 0-0.2Mpa to synthesize the tetraphenylporphyrin. The process has the advantages of uniformly mixing the materials, reducing the equivalence ratio of the materials in the reaction process, improving the usage amount of the catalyst, the conversion rate of the raw materials and the selectivity of the product in the reaction process, reducing the occurrence of side reactions and polymerization reactions, reducing the difficulty of separating and purifying the product and obviously improving the reaction yield.
Description
Technical Field
The invention relates to application of a reflux pipe type reactor in organic synthesis, in particular to a method for carrying out tetraphenylporphyrin reaction by adopting the reflux pipe type reactor, belonging to the field of organic synthesis.
Background
Tetraphenylporphyrin, english name: meso-tetraphenylporphyrine, abbreviated TPP, CAS: 917-23-7, formula C40H33N4The metal complex is one of the most important compounds in porphyrin derivatives, is an important luminescent material, a sensitive material and a semiconductor material, and is widely applied to gas sensors, intelligent materials and sensor technologies.
Originally obtained porphyrins were extracted from the body weight of organisms, and since 1929 Hans Fisher synthesized iron protoporphyrin IX and acquired Nobel prize, porphyrin synthesis research made a major breakthrough. However, the synthesis method is to use natural porphyrin compounds as raw materials and synthesize the porphyrin compounds by known chemical reactions. Alder and 1967 propose that benzaldehyde and pyrrole are used as raw materials, propionic acid is used as a solvent, and the raw materials are refluxed for 30 minutes at 141 ℃ to react, and the yield is nearly 20%. In 1987, Lindsey et al proposed a synthesis method with high yield based on the study of ring and equilibrium reactions and porphyrin biosynthesis, but the reaction steps were many, the conditions were harsh, and large-scale synthesis was difficult. WO2010130065A1 proposes the synthesis in a polymeric oxidation reactor with yields of approximately 32-40%.
The conventional laboratory apparatus and reaction vessel have problems in the reaction such as: the catalyst is used in a large amount in the reaction process, so that waste is caused; increases the selectivity difference of three wastes and regional reaction, and generates more dihydroaryl porphyrin impurities; in the reaction process, because pyrrole is easy to polymerize, the system color is dark red, the acidic filtrate is sticky, the components are complex, the waste liquid cannot be treated, and the like, the overall reaction yield is also low.
Therefore, the process scale-up of the product still has more difficulties, and reaction conditions suitable for industrial scale-up still need to be found.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a more economical and more environment-friendly preparation process which mainly aims at the problem objectively existing in the reaction of the tetraphenylporphyrin.
The initial research found that: the conventional method for synthesizing tetraphenylporphyrin (the yield is about 30-35%) is adopted, the product is filtered, the reaction mother liquor is reused as the reaction solution for synthesizing the product, the reaction yield is obviously reduced and is lower than 23%, the reaction system is detected, the raw material conversion is complete, more tar-like substances and impurities are generated, the analysis and research of the impurities one by one are difficult due to the excessively complex system, and the side products generated in the system have adverse effects on the reaction.
Although the microchannel reactor has the characteristics of 'instant uniform mixing', 'efficient mass and heat transfer' and 'closed reaction system', the synthesis of tetraphenylporphyrin does not complete the reaction instantly, the heating exchange needs a certain time (usually 20-40 minutes), and the effect of the conventional microreactor is not ideal. In the invention, the reflux pipeline reactor is adopted to carry out the reaction of tetraphenylporphyrin, so that a relatively excellent effect is obtained; the process reduces the consumption of raw materials and catalysts, reduces the generation of side reactions, operates the whole reaction closed system, avoids contacting toxic and harmful substances, and is green and environment-friendly.
The invention provides a method for carrying out tetraphenylporphyrin reaction by a reflux pipe type reactor, which comprises the following steps: i.e. benzaldehyde and pyrrole in a molar ratio of 1:1 under the condition of fluidity, using a reflux tubular reactor to carry out condensation reaction at the reaction temperature of 110-.
In the above technical scheme, the reaction flow diagram is shown in figure 1, and the reaction equation is as follows:
the technical scheme adopted by the invention specifically comprises the following steps:
A. connecting the micro-reactor system; B. the reflux pipe type reactor is subjected to back pressure by a back pressure valve, and the pressure in the reflux pipe type reactor system is reached; C. heating the delay pipelines of the micro mixer U and the shell-and-tube reactor to the reaction temperature by a constant temperature bath; D. balancing and calibrating the system; E. connecting two micro-channel reactors in parallel and then connecting the two micro-channel reactors in series with a third micro-channel reactor and a fourth micro-channel reactor; F. pumping mixed liquor of benzaldehyde and pyrrole and protonic acid into A1 and A2 respectively for preheating, then entering a reactor B, C for mixing reaction, simultaneously pumping an oxidant into or introducing C through a feeding pump, and enabling the reacted material to enter a receiving tank for cooling storage for post treatment; G. stopping the pump, cleaning the system, sending the material to a gas phase detection, filtering the material, and pulping and purifying the obtained crude filter cake product by methanol to obtain the high-purity tetraphenylporphyrin.
Further, in the technical scheme, the volume flow ratio of the benzaldehyde and pyrrole mixed solution to the acid or the acid anhydride is 1:3.9-4.6, and the reaction temperature of the reaction module B, C is 120-135 ℃; the reaction retention time is 3-10min, and the volume flow ratio of the mixed solution of benzaldehyde and pyrrole to protonic acid is 1: 3.9-4.6.
Further, in the above technical solution, the acid is selected from acetic acid or propionic acid, and the acid anhydride is selected from acetic anhydride or propionic anhydride. Also, a mixed system of acetic acid/acetic anhydride, propionic acid/propionic anhydride may be used.
Further, in the above technical solution, the preheating temperature in the flow chart is 110-.
Further, in the above technical scheme, the reaction temperature in the flow chart is 120-130 ℃.
Further, in the above technical solution, the oxidant is selected from oxygen, air or nitrobenzene.
Further, in the technical scheme, the molar charge ratio of the benzaldehyde, the pyrrole, the acid and the oxidant is 1:1: 0.5-14: 2-2.3.
Further, in the above technical solution, the purification method is methanol pulping. In order to stably obtain a purity of 99.0% or more, methanol is usually used for beating twice.
Further, in the above technical scheme, the purification method is that the pulping temperature is 0-20 ℃.
The invention has the beneficial effects that:
compared with the prior synthesis method, the invention has the following beneficial effects:
1) the reflux pipe type reactor is a closed system, so that the contact of aldehyde toxic substances can be avoided;
2) the invention can realize the uniform mixing of a non-instantaneous rapid reaction system, can well carry out mass transfer, and has no state of uneven stirring;
3) the conversion rate of the raw materials and the selectivity of the reaction products are improved by at least 15 percent, and the yield is improved by 15 to 25 percent;
4) the equivalence ratio of materials in the reaction process is reduced, the equivalence ratio of one raw material does not need to be increased so as to ensure that the other raw material is fully reacted, and meanwhile, the recovery process of excessive raw materials is avoided, and the production cost is reduced;
5) the use amount of the catalyst in the reaction process is reduced, the waste is avoided, and the method is more environment-friendly;
6) the reaction time can be accurately controlled, and the reaction can be separated from the system for quenching after the reaction is finished, so that the tar formation in the system is avoided.
Drawings
FIG. 1 is a flow diagram of the synthetic reaction described in the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. These examples are to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever. After reading the description of the invention, one skilled in the art can make various changes and modifications to the invention, and such equivalent changes and modifications also fall into the scope of the invention defined by the claims. The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. The reagents and materials described in the following examples are commercially available unless otherwise specified, and the post-treatment method is not limited to the examples of the present invention, and representative examples are given.
Example 1
1) Connecting the A1 and A2 reaction modules in parallel and then sequentially connecting the A1 and A2 reaction modules in series with the B, C reaction modules, and replacing the microchannel reactor with protonic acid; weighing 106g (1mol) of benzaldehyde and 67g (1mol) of pyrrole, mixing to obtain a homogeneous solution, and putting the homogeneous solution into a storage tank V-01, wherein the volume is about 170 mL; weighing 680g of propionic acid, and putting the propionic acid into a storage tank V-02 with the volume of about 681 mL;
2) controlling the volume flow rate of the mixed solution of benzaldehyde and pyrrole to be 2.0mL/min, and pumping the mixed solution into a first reaction module A1 by a pump P-01 to preheat the mixed solution to 110 ℃; controlling the volume flow rate of the propionic acid to be 7.8mL/min, and pumping the propionic acid into a second reaction module A2 by a pump P-02 to preheat for 120 ℃; then the mixture enters a third reaction module B for mixing; 184.5g of nitrobenzene in a pre-storage tank V-03 is pumped in while the mixed material enters a fourth reaction module C; passing through a delay pipeline of a tubular reactor, finishing the reaction for 3min, wherein the reaction temperature is 125 ℃;
3) the reacted material enters a receiving tank V-04, is cooled and stirred, and is sent to HPLC for detection, wherein the conversion rate of benzaldehyde is 86%, and the reaction selectivity is 77%;
4) cooling to 5 deg.C, stirring for 30min, separating out product, filtering to obtain crude tetraphenylporphyrin, adding methanol, heating to 40 deg.C, pulping for 1 hr, cooling to-15 deg.C, and filtering to obtain tetraphenylporphyrin 102.9g with HPLC analysis content of 97.3% and yield of 67%;
5) and (5) stopping the pump and cleaning the system.
Example 2
1) Connecting the A1 and A2 reaction modules in parallel and then sequentially connecting the A1 and A2 reaction modules in series with the B, C reaction modules, and replacing the microchannel reactor with protonic acid; weighing 106g (1mol) of benzaldehyde and 67g (1mol) of pyrrole, mixing to obtain a homogeneous solution, and putting the homogeneous solution into a storage tank V-01, wherein the volume is about 170 mL; weighing 727g of acetic acid, and putting the acetic acid into a storage tank V-02 with the volume of about 693 mL;
2) controlling the volume flow rate of the mixed solution of benzaldehyde and pyrrole to be 2.0mL/min, and enabling the mixed solution to enter a first reaction module A1 through a pump P-01 to be preheated by 120 ℃; controlling the volume flow rate of acetic acid to be 8.2mL/min, and pumping the acetic acid into a second reaction module A2 by a pump P-02 to preheat the acetic acid to 115 ℃; then the mixture enters a third reaction module B for mixing; introducing compressed air into the fourth reaction module C at a speed of 80cm3/min while the mixed materials enter the fourth reaction module C; passing through a delay pipeline of a tubular reactor, finishing for 10min, and controlling the reaction temperature to be 125 ℃;
3) the reacted materials enter a receiving tank V-04, are cooled and stirred, and are sent to LC for detection, wherein the conversion rate of benzaldehyde is 91%, and the reaction selectivity is 81%;
4) cooling to 5 deg.C, stirring for 30min, separating out product, filtering to obtain crude tetraphenylporphyrin, adding methanol, heating to 40 deg.C, pulping for 1 hr, cooling to-15 deg.C, and filtering to obtain 112.1g tetraphenylporphyrin with HPLC analysis content of 98.3% and yield of 73%;
5) and (5) stopping the pump and cleaning the system.
Example 3:
1) connecting the A1 and A2 reaction modules in parallel and then sequentially connecting the A1 and A2 reaction modules in series with the B, C reaction modules, and replacing the microchannel reactor with protonic acid; weighing 106g (1mol) of benzaldehyde and 67g (1mol) of pyrrole, mixing to obtain a homogeneous solution, and putting the homogeneous solution into a storage tank V-01, wherein the volume is about 170 mL; weighing 788g of acetic anhydride, and putting the acetic anhydride into a storage tank V-02 with the volume of about 730 mL;
2) controlling the volume flow rate of the mixed solution of benzaldehyde and pyrrole to be 2.0mL/min, and enabling the mixed solution to enter a first reaction module A1 through a pump P-01 to be preheated by 120 ℃; controlling the volume flow rate of acetic anhydride to be 9.2mL/min, and pumping the acetic anhydride from a pump P-02 into a second reaction module A2 to preheat the acetic anhydride to 115 ℃; then the mixture enters a third reaction module B for mixing; introducing compressed air into the fourth reaction module C at a speed of 30cm3/min while the mixed materials enter the fourth reaction module C; passing through a delay pipeline of a tubular reactor, finishing the reaction for 7min, wherein the reaction temperature is 130 ℃;
3) the reacted materials enter a receiving tank V-04, are cooled and stirred, and are sent to HPLC for detection, wherein the conversion rate of benzaldehyde is 83 percent, and the reaction selectivity is 74 percent;
4) cooling to 5 deg.C, stirring for 30min, separating out product, filtering to obtain crude tetraphenylporphyrin, adding methanol, heating to 40 deg.C, pulping for 1 hr, cooling to-15 deg.C, and filtering to obtain 96.8g tetraphenylporphyrin with HPLC analysis content of 98.1% and yield of 63%;
5) and (5) stopping the pump and cleaning the system.
Example 4
1) Connecting the A1 and A2 reaction modules in parallel and then sequentially connecting the A1 and A2 reaction modules in series with the B, C reaction modules, and replacing the microchannel reactor with protonic acid; weighing 106g (1mol) of benzaldehyde and 67g (1mol) of pyrrole, mixing to obtain a homogeneous solution, and putting the homogeneous solution into a storage tank V-01, wherein the volume is about 170 mL; weighing 677g of propionic anhydride, and placing into a storage tank V-02 with the volume of about 662 mL;
2) controlling the volume flow rate of the mixed solution of benzaldehyde and pyrrole to be 2.0mL/min, and enabling the mixed solution to enter a first reaction module A1 through a pump P-01 to be preheated by 120 ℃; controlling the volume flow rate of propionic anhydride to be 7.2mL/min, and pumping the propionic anhydride from a pump P-02 into a second reaction module A2 to preheat the propionic anhydride to 120 ℃; then the mixture enters a third reaction module B for mixing; 184.5g of nitrobenzene in a pre-storage tank V-03 is pumped in while the mixed material enters a fourth reaction module C; passing through a delay pipeline of a tube array reactor, finishing the reaction for 4min, wherein the reaction temperature is 120 ℃;
3) the reacted materials enter a receiving tank V-04, are cooled and stirred, and are sent to HPLC for detection, wherein the conversion rate of benzaldehyde is 81%, and the reaction selectivity is 69%;
4) cooling to 5 deg.C, stirring for 30min, separating out product, filtering to obtain crude tetraphenylporphyrin, adding methanol, heating to 40 deg.C, pulping for 1 hr, cooling to-15 deg.C, and filtering to obtain 90.6g tetraphenylporphyrin with HPLC analysis content of 97.6% and yield of 59%;
5) and (5) stopping the pump and cleaning the system.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (8)
1. A method for synthesizing tetraphenylporphyrin by a reflux pipe type reactor is characterized by comprising the following steps: benzaldehyde and pyrrole in a molar ratio of 1:1, adopting a reflux pipe type reactor, and controlling the reaction temperature of 110-140 ℃ and the reaction pressure of 0-0.2Mpa to carry out condensation reaction in the presence of acid or acid anhydride and oxidant to generate tetraphenylporphyrin.
2. The method for synthesizing tetraphenylporphyrin in a loop reactor as defined in claim 1, wherein the method comprises the following steps: A. connecting the micro-reactor system; B. the reflux pipe type reactor is subjected to back pressure by a back pressure valve, and the pressure in the reflux pipe type reactor system is reached; C. heating the delay pipelines of the micro mixer U and the shell-and-tube reactor to the reaction temperature by a constant temperature bath; D. balancing and calibrating the system; E. connecting two micro-channel reactors in parallel and then connecting the two micro-channel reactors in series with a third micro-channel reactor and a fourth micro-channel reactor; F. pumping mixed solution of benzaldehyde and pyrrole and acid or anhydride solution into A1 and A2 respectively for preheating, then entering a reactor B, C for mixing reaction, simultaneously pumping an oxidant into C through a feeding pump, feeding the reacted material into a receiving tank for cooling and storing, and carrying out post-treatment; G. stopping the pump, cleaning the system, sending the material to a gas phase detection, filtering the material, and pulping and purifying the obtained crude filter cake product by methanol to obtain the tetraphenylporphyrin.
3. The method for synthesizing tetraphenylporphyrin in a loop reactor of claim 2, wherein: the acid is selected from acetic acid or propionic acid, and the acid anhydride is selected from acetic anhydride or propionic anhydride.
4. The method for synthesizing tetraphenylporphyrin in a loop reactor of claim 2, wherein: the reaction temperature is 120-135 ℃; the reaction retention time is 3-10min, and the volume flow ratio of the mixed solution of benzaldehyde and pyrrole to the acid is 1: 3.9-4.6.
5. The process for the synthesis of tetraphenylporphyrin in a reflux tube reactor as claimed in claim 2, wherein: the preheating temperature in the step F is 110-120 ℃.
6. The process for the synthesis of tetraphenylporphyrin in a reflux tube reactor as claimed in claim 2, wherein: the reaction temperature in step F was 120-130 ℃.
7. The process for the synthesis of tetraphenylporphyrins in a reflux tube reactor as claimed in claim 1 or 2, characterized in that: the oxidant is selected from oxygen, air or nitrobenzene.
8. The process for the synthesis of tetraphenylporphyrin in a reflux tube reactor as claimed in claim 1, wherein: the feeding molar ratio of the benzaldehyde, the pyrrole, the acid or the anhydride to the oxidant is 1:1: 0.5-14: 2-2.3.
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