CN113943493A - Method for synthesizing spirooxazine photochromic dye by using microchannel reactor - Google Patents
Method for synthesizing spirooxazine photochromic dye by using microchannel reactor Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000002994 raw material Substances 0.000 claims abstract description 50
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- -1 nitro, amino Chemical group 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 16
- 150000002367 halogens Chemical group 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 12
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 239000011737 fluorine Substances 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000007970 homogeneous dispersion Substances 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 239000000376 reactant Substances 0.000 abstract description 22
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000001953 recrystallisation Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 31
- 239000000975 dye Substances 0.000 description 23
- 239000003054 catalyst Substances 0.000 description 18
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 16
- YXAOOTNFFAQIPZ-UHFFFAOYSA-N 1-nitrosonaphthalen-2-ol Chemical compound C1=CC=CC2=C(N=O)C(O)=CC=C21 YXAOOTNFFAQIPZ-UHFFFAOYSA-N 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 10
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 230000001105 regulatory effect Effects 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- ZTUKGBOUHWYFGC-UHFFFAOYSA-N 1,3,3-trimethyl-2-methylideneindole Chemical compound C1=CC=C2N(C)C(=C)C(C)(C)C2=C1 ZTUKGBOUHWYFGC-UHFFFAOYSA-N 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- YNMGRZLDRLHRTN-UHFFFAOYSA-N 1,2,3,3-tetramethyl-2h-indole Chemical compound C1=CC=C2C(C)(C)C(C)N(C)C2=C1 YNMGRZLDRLHRTN-UHFFFAOYSA-N 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- FBSPVPGRNVGTBQ-UHFFFAOYSA-N 1-nitrosonaphthalene-2,7-diol Chemical compound C1=CC(O)=C(N=O)C2=CC(O)=CC=C21 FBSPVPGRNVGTBQ-UHFFFAOYSA-N 0.000 description 2
- VDMXGJJMPKAYQP-UHFFFAOYSA-N 5-chloro-1,3,3-trimethyl-2-methylideneindole Chemical compound ClC1=CC=C2N(C)C(=C)C(C)(C)C2=C1 VDMXGJJMPKAYQP-UHFFFAOYSA-N 0.000 description 2
- KSVHNPLBRUHTQA-UHFFFAOYSA-N 5-nitroso-6H-quinolin-5-ol Chemical compound OC1(C=2C=CC=NC=2C=CC1)N=O KSVHNPLBRUHTQA-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- HSGIKWSAFYCPDL-UHFFFAOYSA-N 1',3',3',5',6'-pentamethylspiro[benzo[f][1,4]benzoxazine-3,2'-indole] Chemical compound C1=CC=CC2=C(N=CC3(C(C)(C)C4=CC(C)=C(C)C=C4N3C)O3)C3=CC=C21 HSGIKWSAFYCPDL-UHFFFAOYSA-N 0.000 description 1
- ICAOQPRXCZFWTM-UHFFFAOYSA-N 1',3',3'-trimethyl-6-piperidin-1-yl-6'-(trifluoromethyl)spiro[benzo[f][1,4]benzoxazine-3,2'-indole] Chemical compound CN1C2=CC(C(F)(F)F)=CC=C2C(C)(C)C1(C=NC1=C2C=CC=CC2=2)OC1=CC=2N1CCCCC1 ICAOQPRXCZFWTM-UHFFFAOYSA-N 0.000 description 1
- YAWJWXXKKHOMQT-UHFFFAOYSA-N 1',3',3'-trimethyl-6-piperidin-1-ylspiro[benzo[f][1,4]benzoxazine-3,2'-indole] Chemical compound CN1C2=CC=CC=C2C(C)(C)C1(C=NC1=C2C=CC=CC2=2)OC1=CC=2N1CCCCC1 YAWJWXXKKHOMQT-UHFFFAOYSA-N 0.000 description 1
- CQTRKDFIQFOAQV-UHFFFAOYSA-N 1',3',3'-trimethylspiro[benzo[f][1,4]benzoxazine-3,2'-indole] Chemical compound C1=CC=CC2=C(N=CC3(C(C)(C)C4=CC=CC=C4N3C)O3)C3=CC=C21 CQTRKDFIQFOAQV-UHFFFAOYSA-N 0.000 description 1
- IPGFMOWJULBATG-UHFFFAOYSA-N 1',3',3'-trimethylspiro[benzo[f][1,4]benzoxazine-3,2'-indole]-9-ol Chemical compound C1=CC(O)=CC2=C(N=CC3(C(C)(C)C4=CC=CC=C4N3C)O3)C3=CC=C21 IPGFMOWJULBATG-UHFFFAOYSA-N 0.000 description 1
- JSULBGPSGDBITL-UHFFFAOYSA-N 1,3,3,5,6-pentamethyl-2-methylideneindole Chemical compound CC1=C(C)C=C2N(C)C(=C)C(C)(C)C2=C1 JSULBGPSGDBITL-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- GYUZHNKXZJGPSC-UHFFFAOYSA-N 5'-chloro-1',3',3'-trimethyl-6-piperidin-1-ylspiro[benzo[f][1,4]benzoxazine-3,2'-indole] Chemical compound CN1C2=CC=C(Cl)C=C2C(C)(C)C11OC2=C(N=C1)C1=C(C=CC=C1)C(=C2)N1CCCCC1 GYUZHNKXZJGPSC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B19/00—Oxazine dyes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/10—Spiro-condensed systems
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D498/20—Spiro-condensed systems
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- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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Abstract
The invention relates to a method for synthesizing spirooxazine photochromic dye by using a microchannel reactor. In the coupling ring forming process at the later stage of dye synthesis, after the temperature of a mobile phase system containing reaction raw materials is respectively adjusted to the reaction temperature by a pre-reaction system, the mobile phases are respectively pumped into a microchannel reactor by a constant flow pump for mixed temperature control reaction to obtain a solution containing the photochromic dye, and the photochromic dye is obtained by concentration, recrystallization, decoloration and drying. The method ensures the sufficient mixing of reactants and the accuracy of temperature control by utilizing the higher mixing and heat exchange efficiency of the micro-channel, has good energy-saving effect, reduces the production cost, has high product purity, reduces the subsequent treatment difficulty, can repeatedly utilize the mobile phase, is convenient for large-scale production, and has wide application prospect.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a method for synthesizing spirooxazine photochromic dye by using a microchannel reactor.
Background
Photochromic materials are materials that change color when excited by a light source. Can be divided into two main categories of inorganic photochromic materials and organic photochromic materials. The organic photochromic materials have good performances in the fields of information storage, decorative packaging, textile clothing, eye lenses, anti-counterfeiting printing and the like due to the advantages of various types, various colors and the like, and the spirooxazine photochromic materials have good color change speed and bright color expression, so that the organic photochromic materials are concerned by researchers in various organic photochromic dyes.
However, the synthesis of the photochromic dye at the present stage still adopts the traditional organic synthesis method, the reaction raw materials are added into the reactor and mixed by using a stirrer under the atmosphere of protective gas, the mixing efficiency is lower, and due to the problem of heat conduction efficiency, the temperature control of the system in the reactor is not sensitive and accurate enough, the side reactions are more, the difficulty of later purification is high, some side reaction products are difficult to remove, and the color of the final product is influenced. Meanwhile, in order to reduce the occurrence of side reactions and improve the reaction efficiency, the reaction raw materials need to be added in batches in the synthesis process of the photochromic dye, so that the operation is complicated, the control difficulty is increased, and the large-scale production is not facilitated.
Disclosure of Invention
In order to solve the defects of low reactant mixing efficiency, insensitive and accurate temperature control of a reaction system, more side reactions, complex operation, inconvenience for large-scale production and the like, the invention introduces the microchannel reactor into the alkynol coupling reaction in the preparation process of the photochromic dye and provides a method for synthesizing the photochromic dye by utilizing the microchannel reactor.
A method for synthesizing spirooxazine photochromic dye by using a microchannel reactor is characterized by comprising the following steps: respectively dissolving or uniformly dispersing compounds serving as reaction raw materials in a mobile phase to prepare corresponding mobile phase solution, adjusting the temperature of the system to the reaction temperature by a pre-reaction system, respectively injecting the mobile phase solution into a microchannel reactor through a constant flow pump to perform mixing temperature control reaction to obtain solution containing the target optically variable dye, concentrating, recrystallizing, decoloring and drying the solution to obtain the photochromic dye, wherein the mobile phase can be recycled in the subsequent treatment process;
the structural formula of the spirooxazine photochromic dye is as follows:
wherein R1, R2 and R3 may be the same or different and each independently represents hydrogen, C1-C8 alkyl, C1-C6 alkoxy or halogenated (C1-C8) alkane, and the halogenated group is fluorine, chlorine or bromine.
R4 represents hydrogen, halogen, C1-C8 alkyl, C1-C6 alkoxy, halo (C1-C8) alkane, hydroxyl, nitro, amino or carboxyl, the halogen or halo group is fluorine, chlorine or bromine, and a is 1, 2 or 3.
R5 and R6 which may be the same or different each independently represent hydrogen, halogen, C1-C8 alkyl, C1-C6 alkoxy, halo (C1-C8) alkane, hydroxyl, nitro, amino, carboxyl, a five-or six-membered cyclic group containing oxygen, nitrogen and sulfur atoms, benzopyridyl or benzopyrrolidinyl, wherein the halogen or halo group is fluorine, chlorine or bromine, and b and C are 1, 2 or 3.
Ring A is a benzene ring or a heterocyclic ring containing a nitrogen, oxygen or sulfur atom.
One of the compounds used as the reaction raw materials has the following structural formula:
wherein R1, R2 and R3 may be the same or different and each independently represents hydrogen, C1-C8 alkyl, C1-C6 alkoxy or halogenated (C1-C8) alkane, and the halogenated group is fluorine, chlorine or bromine;
r4 represents hydrogen, halogen, C1-C8 alkyl, C1-C6 alkoxy, halo (C1-C8) alkane, hydroxyl, nitro, amino or carboxyl, wherein the halogen or halo group is fluorine, chlorine or bromine, and a is 1, 2 or 3;
the structural formula of another compound used as the reaction raw material is shown as follows:
r7 and R8, which may be the same or different, each independently represent hydrogen, halogen, C1-C8 alkyl, C1-C6 alkoxy, halo (C1-C8) alkane, hydroxy, nitro, amino or carboxy, R8 may also represent substituted allyl, formyl, cyano and sulfonic acid groups, the halogen or halo groups are fluorine, chlorine or bromine, d and e are 1, 2 or 3.
Ring a is a carbocyclic ring, a benzene ring, or a heterocyclic ring containing nitrogen, oxygen, or sulfur atoms.
The mobile phase is at least one of methanol, ethanol, benzene, toluene, xylene or cyclohexane.
The microchannel reactor is at least one of a tubular microchannel reactor or a surface microchannel reactor, and is made of pressure-resistant materials easy to conduct heat.
The temperature control reaction temperature in the microchannel reactor is 40-110 ℃.
The reaction time in the microchannel reactor is 1-8 h.
The reaction raw material mobile phase solution is a uniform dispersion liquid with the mass fraction of 5-40%.
The invention has the advantages and beneficial effects that:
1. the microchannel reactor is used in the synthesis process of the photochromic dye, so that the reaction mixing and heat exchange efficiency is improved, the full reaction and the rapid and accurate temperature control in the reaction process are facilitated, the reaction time is shortened, the reaction efficiency and the product purity are obviously improved, and the subsequent product treatment difficulty is reduced.
2. The reaction is carried out in the microchannel reactor, so that the reaction condition that nitrogen needs to be introduced into the reactor for protection in the traditional synthetic method is avoided, and the large-scale production is facilitated.
2. The production is carried out by adopting a flowing feeding mode, the production scale is flexible and controllable, and after the reaction is finished, the mobile phase solution can be recycled through a concentration process, so that the production cost is effectively reduced.
The method has the advantages of easily controlled reaction conditions, energy conservation, emission reduction, good continuous productivity, convenience for large-scale production and wide application prospect.
Drawings
FIG. 1 is a schematic flow chart of synthesis of photochromic dye by a microchannel reactor.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
1,3, 3-trimethyl-2-methylene indoline and 1-nitroso-2-naphthol are used as raw materials, a mobile phase is ethanol, and the mass fraction of the mobile phase containing reaction raw materials is 20%. And (3) pre-adjusting the temperature of the mobile phase system to 70 ℃, regulating and controlling the speed according to the molar ratio of the reactant raw materials of 1:1 by a constant flow pump, respectively injecting the reactant raw materials into a microchannel reactor for mixing, and reacting at 70 ℃ for 2 hours to obtain a solution containing the target optically variable dye, wherein the reaction is shown as follows. The solution is concentrated, recrystallized, decolorized and dried to obtain a light yellow powder product. The melting point of the product is 127-130 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 1,3, 3-trimethyl-spiro [ indoline-2, 3-naphtho [2,1-b ] [1,4] oxazine ].
Example 2
1,3, 3-trimethyl-2-methylene indoline, 5-nitroso-5 hydroxyquinoline and piperidine are used as raw materials, a mobile phase is ethanol, and the mass fraction of the mobile phase containing reaction raw materials is 40%. Pre-adjusting the temperature of the mobile phase system to 50 ℃, regulating and controlling the speed of the reactant raw materials and the catalyst to be 1:1:1 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, mixing the mobile phase containing 5-nitroso-5 hydroxyquinoline and piperidine for reaction for 10min, mixing the mobile phase containing 1,3, 3-trimethyl-2-methylindoline, and reacting for 8h at 50 ℃ to obtain a solution containing the target photochromic dye, wherein the reaction is shown as follows. And concentrating, recrystallizing, decoloring and drying the solution to obtain a light orange powder product. The melting point of the product is 200-202 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 1,3, 3-trimethyl-6-piperidyl-spiro [ indoline-2, 3-quinolino [2,1-b ] [1,4] oxazine ].
Example 3
1,3, 3-trimethyl-2-methylene indoline, 1-nitroso-2-naphthol and piperidine are used as raw materials, a mobile phase is toluene, and the mass fraction of the mobile phase containing reaction raw materials is 30%. Pre-adjusting the temperature of the mobile phase system to 110 ℃, regulating and controlling the speed of the reactant raw materials and the catalyst to be 1:1:1 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, mixing the mobile phase containing 1-nitroso-2-naphthol and piperidine for reaction for 3min, mixing the mobile phase containing 1,3, 3-trimethyl-2-methylindoline, and reacting for 3h at 110 ℃ to obtain a solution containing the target photochromic dye, wherein the reaction is shown as follows. The solution is concentrated, recrystallized, decolorized and dried to obtain a white powder product. The melting point of the product is 238-240 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 6' -piperidyl-1, 3, 3-trimethyl-spiro [ indoline-2, 3-naphtho [2,1-b ] [1,4] oxazine ].
Example 4
1,3, 3-trimethyl-2-methylene indoline and 4-cyano-1-nitroso-2-naphthol are used as raw materials, a mobile phase is toluene, and the mass fraction of the mobile phase containing the reaction raw materials is 5%. And (3) pre-adjusting the temperature of the mobile phase system to 90 ℃, regulating and controlling the speed according to the molar ratio of the reactant raw materials to the catalyst of 1:1 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, and reacting for 5 hours at 90 ℃ to obtain a solution containing the target photochromic dye, wherein the reaction is shown as follows. The solution is concentrated, recrystallized, decolorized and dried to obtain a light yellow powder product. The melting point of the product is 158-160 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 6-cyano-1, 3, 3-trimethyl-spiro [ indoline-2, 3-naphtho [2,1-b ] [1,4] oxazine ].
Example 5
5-chloro-1, 3, 3-trimethyl-2-methylene indoline, 1-nitroso-2-naphthol and piperidine are used as raw materials, a mobile phase is toluene, and the mass fraction of the mobile phase containing reaction raw materials is 25%. Pre-adjusting the temperature of the mobile phase system to 70 ℃, regulating and controlling the speed of the reactant raw materials and the catalyst to be 1:1:1 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, mixing the mobile phase containing 1-nitroso-2-naphthol and piperidine for reaction for 5min, mixing the mobile phase containing 5-chloro-1, 3, 3-trimethyl-2-methylene indoline into the reactor, and reacting for 4h at 70 ℃ to obtain a solution containing the target photochromic dye, wherein the reaction is shown in the following schematic diagram. The solution is concentrated, recrystallized, decolorized and dried to obtain a white powder product. The melting point of the product is 230-232 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 5-chloro-1, 3, 3-trimethyl-6' -piperidyl-spiro [ indoline-2, 3-naphtho [2,1-b ] [1,4] oxazine ].
Example 6
1,3, 3-trimethyl-2-methylene indoline, 1-nitroso-2-naphthol and quinoline are taken as raw materials, a mobile phase is benzene, and the mass fraction of the mobile phase containing the reaction raw materials is 10%. Pre-adjusting the temperature of the mobile phase system to 90 ℃, regulating and controlling the speed of the reactant raw materials and the catalyst to be 1:1:1 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, mixing the mobile phase containing 1-nitroso-2-naphthol and quinoline for reaction for 10min, mixing the mobile phase containing 1,3, 3-trimethyl-2-methylindoline, and reacting for 1h at 90 ℃ to obtain a solution containing the target photochromic dye, wherein the reaction is shown as follows. The solution is concentrated, recrystallized, decolored and dried to obtain a light yellow powder product. The melting point of the product is 259-261 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 6 '-quinolyl-1, 3, 3-trimethyl-6' -piperidyl-spiro [ indoline-2, 3-naphtho [2,1-b ] [1,4] oxazine ].
Example 7
3,3,5, 6-tetramethyl-2-methylene-1-n-propyl indoline and 1-nitroso-2-naphthol are used as raw materials, a mobile phase is ethanol, and the mass fraction of the mobile phase containing reaction raw materials is 20%. And (3) pre-adjusting the temperature of the mobile phase system to 40 ℃, regulating and controlling the speed according to the molar ratio of the reactant raw materials to the catalyst of 1:1 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, and reacting for 5 hours at 40 ℃ to obtain a solution containing the target photochromic dye, wherein the reaction is shown as follows. The solution is concentrated, recrystallized, decolored and dried to obtain a light yellow powder product. The melting point of the product is 130-132 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 3,3,5, 6-tetramethyl-1-n-propyl-spiro [ indoline-2, 3-naphtho [2,1-b ] [1,4] oxazine ].
Example 8
1,3, 3-trimethyl-2-methylene-6-trifluoromethyl indoline, 1-nitroso-2-naphthol and piperidine are used as raw materials, a mobile phase is methanol, and the mass fraction of the mobile phase containing reaction raw materials is 25%. Pre-adjusting the temperature of the mobile phase system to 45 ℃, regulating and controlling the speed of the reactant raw materials and the catalyst to be 1:1:1 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, mixing the mobile phase containing 1-nitroso-2-naphthol and piperidine for reaction for 15min, mixing the mobile phase containing 1,3, 3-trimethyl-2-methylene-6-trifluoromethyl indoline, and reacting for 6h at 45 ℃ to obtain a solution containing the target photochromic dye, wherein the reaction is shown as follows. The solution is concentrated, recrystallized, decolorized and dried to obtain a light pink powder product. The melting point of the product is 219-226 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 1,3, 3-trimethyl-6' -piperidyl-6-trifluoromethyl-spiro [ indoline-2, 3-naphtho [2,1-b ] [1,4] oxazine ].
Example 9
1,3, 3-trimethyl-2-methylene indoline and 1-nitroso-2, 7-dihydroxy naphthalene are taken as raw materials, the mobile phase is ethanol, and the mass fraction of the mobile phase containing the reaction raw materials is 20%. And (3) pre-adjusting the temperature of the mobile phase system to 60 ℃, regulating and controlling the speed according to the molar ratio of the reactant raw materials to the catalyst of 1:1 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, and reacting for 2 hours at 60 ℃ to obtain a solution containing the target photochromic dye, wherein the reaction is shown as follows. The solution is concentrated, recrystallized, decolored and dried to obtain a light yellow powder product. The nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 1,3, 3-trimethyl-9' -hydroxy-spiro [ indoline-2, 3-naphtho [2,1-b ] [1,4] oxazine ].
Example 10
1,3,3,5, 6-pentamethyl-2-methylene indoline and 1-nitroso-2, 7-dihydroxy naphthalene are taken as raw materials, a mobile phase is ethanol, and the mass fraction of the mobile phase containing reaction raw materials is 20%. And (3) pre-adjusting the temperature of the mobile phase system to 60 ℃, regulating and controlling the speed according to the molar ratio of the reactant raw materials to the catalyst of 1:1 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, and reacting for 2 hours at 60 ℃ to obtain a solution containing the target photochromic dye, wherein the reaction is shown as follows. The solution was concentrated, recrystallized, decolorized and dried to yield a yellow powder product. The melting point of the product is 204-206 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 1,3,3,5, 6-pentamethyl-spiro [ indoline-2, 3-naphtho [2,1-b ] [1,4] oxazine ].
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only illustrative of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for synthesizing spirooxazine photochromic dye by using a microchannel reactor is characterized by comprising the following steps: respectively dissolving or uniformly dispersing compounds serving as reaction raw materials in a mobile phase to prepare corresponding mobile phase solution, adjusting the temperature of the system to the reaction temperature by a pre-reaction system, respectively injecting the mobile phase solution into a microchannel reactor by a constant flow pump to perform mixing temperature control reaction to obtain solution containing the target photochromic dye, concentrating, recrystallizing, decoloring and drying the solution to obtain the photochromic dye, wherein the mobile phase can be recycled in the subsequent treatment process.
2. The method according to claim 1, wherein the spirooxazine photochromic dye has the following structural formula:
wherein R1, R2 and R3 may be the same or different and each independently represents hydrogen, C1-C8 alkyl, C1-C6 alkoxy or halogenated (C1-C8) alkane, and the halogenated group is fluorine, chlorine or bromine;
r4 represents hydrogen, halogen, C1-C8 alkyl, C1-C6 alkoxy, halo (C1-C8) alkane, hydroxyl, nitro, amino or carboxyl, wherein the halogen or halo group is fluorine, chlorine or bromine, and a is 1, 2 or 3;
r5 and R6 which may be the same or different each independently represent hydrogen, halogen, C1-C8 alkyl, C1-C6 alkoxy, halo (C1-C8) alkane, hydroxyl, nitro, amino, carboxyl, a five-or six-membered cyclic group containing oxygen, nitrogen and sulfur atoms, benzopyridyl or benzopyrrolidinyl, wherein the halogen or halo group is fluorine, chlorine or bromine, and b and C are 1, 2 or 3;
ring A is a benzene ring or a heterocyclic ring containing a nitrogen, oxygen or sulfur atom.
3. The method of claim 1, wherein one of the compounds used as the starting material is represented by the following structural formula:
wherein R1, R2 and R3 may be the same or different and each independently represents hydrogen, C1-C8 alkyl, C1-C6 alkoxy or halogenated (C1-C8) alkane, and the halogenated group is fluorine, chlorine or bromine;
r4 represents hydrogen, halogen, C1-C8 alkyl, C1-C6 alkoxy, halo (C1-C8) alkane, hydroxyl, nitro, amino or carboxyl, wherein the halogen or halo group is fluorine, chlorine or bromine, and a is 1, 2 or 3;
the structural formula of another compound used as the reaction raw material is shown as the following figure:
r7 and R8, which may be the same or different, each independently represent hydrogen, halogen, C1-C8 alkyl, C1-C6 alkoxy, halo (C1-C8) alkane, hydroxy, nitro, amino or carboxy, R8 may also represent substituted allyl, formyl, cyano and sulfonic acid groups, the halogen or halo groups are fluorine, chlorine or bromine, d and e are 1, 2 or 3;
ring A is a benzene ring or a heterocyclic ring containing a nitrogen, oxygen or sulfur atom.
4. The method of claim 1, wherein the mobile phase is at least one of methanol, ethanol, benzene, toluene, xylene, or cyclohexane.
5. The method of claim 1, wherein the microchannel reactor is at least one of a tubular microchannel reactor or a planar microchannel reactor, and the reactor is constructed of a pressure resistant material that is readily thermally conductive.
6. The method according to claim 1, wherein the temperature of the temperature-controlled reaction in the microchannel reactor is 40 to 110 ℃;
the reaction time in the microchannel reactor is 1-8 h.
7. The method according to claim 1, wherein the reaction raw material mobile phase solution is a homogeneous dispersion liquid with a mass fraction of 5-40%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1369493A (en) * | 2002-02-25 | 2002-09-18 | 四川大学 | Process for quickly synthesizing photochromic spirooxazine by microwave |
| US20060115768A1 (en) * | 2004-11-30 | 2006-06-01 | Fuji Photo Film Co. Ltd | Lithographic printing plate precursor, plate-making method, and lithographic printing method |
| CN103539770A (en) * | 2013-10-08 | 2014-01-29 | 常州大学 | Continuous reaction technological method for preparing epsilon-caprolactone, and microchannel reaction equipment |
| CN104892631A (en) * | 2015-06-04 | 2015-09-09 | 中国中化股份有限公司 | Sulfo group-containing spirooxazine type photochromic compound as well as preparation method and application thereof |
-
2020
- 2020-07-18 CN CN202010694883.6A patent/CN113943493A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1369493A (en) * | 2002-02-25 | 2002-09-18 | 四川大学 | Process for quickly synthesizing photochromic spirooxazine by microwave |
| US20060115768A1 (en) * | 2004-11-30 | 2006-06-01 | Fuji Photo Film Co. Ltd | Lithographic printing plate precursor, plate-making method, and lithographic printing method |
| CN103539770A (en) * | 2013-10-08 | 2014-01-29 | 常州大学 | Continuous reaction technological method for preparing epsilon-caprolactone, and microchannel reaction equipment |
| CN104892631A (en) * | 2015-06-04 | 2015-09-09 | 中国中化股份有限公司 | Sulfo group-containing spirooxazine type photochromic compound as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 吴迪等: "微反应器技术及其研究进展", 中国陶瓷工业, vol. 25, no. 5, pages 19 - 26 * |
| 孙宾宾: "介绍一个有机化学实验――光致变色化合物螺噁嗪的合成", 广州化工, vol. 46, no. 7, pages 117 - 118 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115448929A (en) * | 2022-10-24 | 2022-12-09 | 阜阳欣奕华制药科技有限公司 | Preparation method and application of compound |
| CN115448929B (en) * | 2022-10-24 | 2023-08-11 | 阜阳欣奕华制药科技有限公司 | Preparation method and application of compound |
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