CN113943267A - Method for synthesizing naphthopyran photochromic dye by using microchannel reactor - Google Patents
Method for synthesizing naphthopyran photochromic dye by using microchannel reactor Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- VCMLCMCXCRBSQO-UHFFFAOYSA-N 3h-benzo[f]chromene Chemical compound C1=CC=CC2=C(C=CCO3)C3=CC=C21 VCMLCMCXCRBSQO-UHFFFAOYSA-N 0.000 title claims description 5
- 239000002994 raw material Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 55
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 16
- 125000005843 halogen group Chemical group 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 7
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 229940126062 Compound A Drugs 0.000 claims description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 125000005157 alkyl carboxy group Chemical group 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims 1
- 239000000376 reactant Substances 0.000 abstract description 26
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 238000001953 recrystallisation Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 39
- 239000000975 dye Substances 0.000 description 26
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 15
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 230000001276 controlling effect Effects 0.000 description 12
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 230000001105 regulatory effect Effects 0.000 description 12
- -1 3, 3-bis (2, 4-dimethoxyphenyl) -3H-naphtho [1,2-b ] pyran Chemical compound 0.000 description 9
- GFSXWQUSLTVUBW-UHFFFAOYSA-N 10bh-benzo[h]chromene Chemical compound C1=CC=C2C3OC=CC=C3C=CC2=C1 GFSXWQUSLTVUBW-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- RFNDMLXNYMQMGN-UHFFFAOYSA-N 1,1-bis(4-methoxyphenyl)prop-2-yn-1-ol Chemical compound C1=CC(OC)=CC=C1C(O)(C#C)C1=CC=C(OC)C=C1 RFNDMLXNYMQMGN-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XBXZVUUYRXBUOL-UHFFFAOYSA-N 1,1-bis(2,4-dimethoxyphenyl)prop-2-yn-1-ol Chemical compound COC1=CC(OC)=CC=C1C(O)(C#C)C1=CC=C(OC)C=C1OC XBXZVUUYRXBUOL-UHFFFAOYSA-N 0.000 description 1
- UWNYADTZRSHNGM-UHFFFAOYSA-N 2,2-diphenylbenzo[h]chromene Chemical compound O1C(C2=CC=CC=C2C=C2)=C2C=CC1(C=1C=CC=CC=1)C1=CC=CC=C1 UWNYADTZRSHNGM-UHFFFAOYSA-N 0.000 description 1
- VXXBEDBHOSBARI-UHFFFAOYSA-N 2,3-dimethoxy-7,7-dimethyl-9-(trifluoromethyl)benzo[c]fluoren-5-ol Chemical compound C1=C(C(F)(F)F)C=C2C(C)(C)C3=CC(O)=C(C=C(C(OC)=C4)OC)C4=C3C2=C1 VXXBEDBHOSBARI-UHFFFAOYSA-N 0.000 description 1
- FMDOHARAOOSWCB-UHFFFAOYSA-N 2,3-dimethoxy-7,7-dimethylbenzo[c]fluoren-5-ol Chemical compound C1=CC=C2C(C)(C)C3=CC(O)=C(C=C(C(OC)=C4)OC)C4=C3C2=C1 FMDOHARAOOSWCB-UHFFFAOYSA-N 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- UHGDSDBRFRGOGI-UHFFFAOYSA-N COC1=CC2=C(C(=CC=3C(C=4C=CC=CC=4C2=3)(O)C)O)C=C1OC Chemical compound COC1=CC2=C(C(=CC=3C(C=4C=CC=CC=4C2=3)(O)C)O)C=C1OC UHGDSDBRFRGOGI-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000234314 Zingiber Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000005805 dimethoxy phenyl group Chemical group 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000008397 ginger Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002360 preparation method Methods 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
- 239000004753 textile Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention relates to a method for synthesizing photochromic dye by using a microchannel reactor. In the alkynol coupling reaction, after the temperature of a mobile phase system respectively containing reaction raw materials is adjusted to the reaction temperature through a pre-reaction system, the mobile phases are respectively pumped into a microchannel reactor by a constant flow pump to carry out mixing temperature control reaction to obtain a solution containing the photochromic dye, and the photochromic dye is obtained through concentration, recrystallization, decoloration and drying. The method ensures the precision of the full mixing and temperature control of reactants by utilizing the higher mixing and heat exchange efficiency of the microchannel, has good energy-saving effect, can repeatedly utilize the mobile phase, reduces the production cost, has high product purity, reduces the subsequent treatment difficulty, 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 naphthopyran 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 pyran photochromic materials are widely concerned by researchers in various organic photochromic dyes due to good color change performances and excellent fatigue resistance.
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, 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 purification difficulty at the later stage is large, 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 naphthopyran photochromic dye by using a microchannel reactor comprises the following steps: respectively dissolving or uniformly dispersing a compound A and a compound B as reaction raw materials and a catalyst in a mobile phase to prepare corresponding mobile phase solutions, adjusting the system temperature of the mobile phase solutions to the reaction temperature through a pre-reaction system, respectively injecting the mobile phase solutions into a microchannel reactor through a constant flow pump to perform mixing temperature control reaction to obtain a solution containing the target optically variable dye, and concentrating, recrystallizing, decoloring and drying the solution to obtain the photochromic dye.
The purity of the photochromic dye product is determined to be more than 99.5% by high performance liquid chromatography, and the structure of the photochromic dye product is determined by melting point and nuclear magnetic resonance spectrogram.
The structural formula of the compound A is shown as follows:
wherein R1, R2, R3 and R4 may be the same OR different and each independently represents any one of hydrogen, halogen, C1-C8 alkyl, C1-C6 alkoxy, halo (C1-C8) alkane, hydroxy C1-C6 alkoxy (C1-C8) alkyl OR-OR, wherein R is C1-C6 alkoxy (C1-C8) alkyl, and the halogen OR halo group is fluorine, chlorine OR bromine.
The structural formula of the compound B is shown as follows:
Wherein, R5, R6, R7 and R8 may be the same OR different, each independently represents hydrogen, halogen, C1 to C8 alkyl, C1 to C6 alkoxy, halo (C1 to C8) alkyl, hydroxy, C1 to C6 alkoxy (C1 to C8) alkyl, C1 to C4 alkylcarboxyl, halo C1 to C4 alkylcarboxyl, substituted OR unsubstituted phenyl, -OR ', OR-oc (o) X, wherein the substituent of phenyl is C1 to C4 alkyl, C1 to C4 alkoxy OR halogen, R' is C1 to C6 alkoxy (C1 to C8) alkyl, X is (C1 to C8) alkyl OR halo (C1 to C8) alkyl, said halogen OR halo group is fluorine, chlorine OR bromine, wherein a, b, C and d are each 1,2 OR 3.
The structural formula of the compound B is shown as follows:
wherein R9, R10, R11 and R12 may be the same OR different, each independently represents hydrogen, halogen, C1-C8 alkyl, C1-C6 alkoxy, halo (C1-C8) alkane, hydroxy, C1-C6 alkoxy (C1-C8) alkyl OR-OR ", wherein R" is C1-C6 alkoxy (C1-C8) alkyl, said halogen OR halo is fluorine, chlorine OR bromine, wherein e and f are each 1,2 OR 3.
The catalyst is at least one of p-toluenesulfonic acid and dodecylbenzene sulfonic acid.
The mobile phase is at least one of benzene, toluene, xylene, tetrahydrofuran 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 0.5-5 h.
The mobile phase solution of the compound A and the compound B is a uniform dispersion liquid with the mass fraction of 5-40%, the mobile phase solution of the catalyst is a uniform dispersion liquid with the mass fraction of 1-1%, and the catalyst can also be added into the mobile phase solution of the compound A or the compound B.
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 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, 1-di (4-methoxyphenyl) -2-propyne-1-ol and 1-phenyl-2-methyl carboxylate-4-naphthol are used as raw materials, dodecylbenzene sulfonic acid is used as a catalyst, a mobile phase is tetrahydrofuran, the mass fraction of the mobile phase containing the reaction raw materials is 20%, and the mass fraction of the mobile phase containing the catalyst is 1 per thousand. And (3) pre-adjusting the temperature of the mobile phase system to 50 ℃, regulating and controlling the speed according to the molar ratio of the reactant raw materials to the catalyst of 1:1:0.01 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, and reacting for 1h at 50 ℃ to obtain a solution containing the target optically variable dye, wherein the reaction formula 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 170-172 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 2, 2-bis (4-methoxyphenyl) -5-carboxylic acid methyl ester-6-phenyl-2H-naphtho [1,2-b ] pyran.
Example 2
1, 1-diphenyl-2-propyne-1-alcohol and 1-naphthol are used as raw materials, dodecylbenzene sulfonic acid is used as a catalyst, a mobile phase is toluene, the mass fraction of the mobile phase containing reaction raw materials is 40%, and the mass fraction of the mobile phase containing the catalyst is 5 per mill. And (3) pre-adjusting the temperature of the mobile phase system to 80 ℃, regulating and controlling the speed according to the molar ratio of the reactant raw materials to the catalyst of 1:1:0.05 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 80 ℃ to obtain a solution containing the target optically variable dye, wherein the reaction formula 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 150-152 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 2, 2-diphenyl-2H-naphtho [1,2-b ] pyran.
Example 3
1, 1-di (2, 4-dimethoxyphenyl) -2-propyne-1-ol and 2-naphthol are used as raw materials, p-toluenesulfonic acid is used as a catalyst, a mobile phase is benzene, the mass fraction of the mobile phase containing reaction raw materials is 30%, and the mass fraction of the mobile phase containing the catalyst is 1%. 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 1:1:0.03 by using 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 optically variable dye, wherein the reaction formula is shown as follows. The solution is concentrated, recrystallized, decolorized and dried to obtain a meat-colored powder product. The melting point of the product is 157-159 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 3, 3-bis (2, 4-dimethoxyphenyl) -3H-naphtho [1,2-b ] pyran.
Example 4
1, 1-di (4-methoxyphenyl) -2-propyne-1-alcohol and 1-acetoxyl-4-hydroxy-2-methyl naphthoate are taken as raw materials, p-toluenesulfonic acid is taken as a catalyst, a mobile phase is cyclohexane, the mass fraction of the mobile phase containing reaction raw materials is 10%, and the mass fraction of the mobile phase containing the catalyst is 8 per thousand. 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 to the catalyst of 1:1:0.1 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, and reacting for 4 hours at 70 ℃ to obtain a solution containing the target optically variable dye, wherein the reaction formula 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 201-203 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 2, 2-bis (dimethoxyphenyl) -5-methyl formate-6-acetoxyl-2H-naphtho [1,2-b ] pyran.
Example 5
1, 1-di (4-methoxyphenyl) -2-propyne-1-alcohol and 7-butoxy-3, 7, 9-trimethyl-5-hydroxy-7H-benzo [ c ] -fluorene are used as raw materials, dodecylbenzene sulfonic acid is used as a catalyst, a mobile phase is xylene, the mass fraction of the mobile phase containing reaction raw materials is 5%, and the mass fraction of the mobile phase containing the catalyst is 3 per mill. And (3) pre-adjusting the temperature of the mobile phase system to 110 ℃, regulating and controlling the speed according to the molar ratio of the reactant raw materials to the catalyst of 1:1:0.01 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, and reacting for 0.5h at 110 ℃ to obtain a solution containing the target photochromic dye, wherein the reaction formula is shown as follows. The solution is concentrated, recrystallized, decolorized and dried to obtain a light purple powder product. The melting point of the product is 168-170 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 3, 3-bis (4-methoxyphenyl) -6,11, 13-trimethyl-13-butoxy-indeno [1,2-f ] naphtho [1,2-b ] pyran.
Example 6
1, 1-di (4-methoxyphenyl) -2-propyne-1-alcohol and 3,7,7, 9-tetramethyl-5-hydroxy-7H-benzo [ c ] -fluorene are used as raw materials, p-toluenesulfonic acid is used as a catalyst, a mobile phase is dimethylbenzene, the mass fraction of the mobile phase containing reaction raw materials is 15%, and the mass fraction of the mobile phase containing the catalyst is 1 per thousand. 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 1:1:0.01 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, and reacting for 4 hours at 90 ℃ to obtain a solution containing the target optically variable dye, wherein the reaction formula 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 246-248 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 3, 3-bis (4-methoxyphenyl) -6,11,13, 13-tetramethyl-indeno [1,2-f ] naphtho [1,2-b ] pyran.
Example 7
1, 1-di (4-methoxyphenyl) -2-propyne-1-alcohol and 2, 3-dimethoxy-7, 7-dimethyl-5-hydroxy-7H-benzo [ c ] -fluorene are used as raw materials, p-toluenesulfonic acid is used as a catalyst, a mobile phase is xylene, the mass fraction of the mobile phase containing reaction raw materials is 25%, and the mass fraction of the mobile phase containing the catalyst is 5 per thousand. And (2) pre-adjusting the temperature of the mobile phase system to 110 ℃, regulating and controlling the speed according to the molar ratio of the reactant raw materials to the catalyst of 1:1:0.01 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 110 ℃ to obtain a solution containing the target optically variable dye, wherein the reaction formula is shown as follows. The solution is concentrated, recrystallized, decolored and dried to obtain a ginger yellow powder product. The melting point of the product is 246-248 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 3, 3-bis (4-methoxyphenyl) -6, 7-dimethoxy-13, 13-dimethyl-indeno [1,2-f ] naphtho [1,2-b ] pyran.
Example 8
1, 1-di (4-methoxyphenyl) -2-propyne-1-alcohol and 2, 3-dimethoxy-7-methyl-5, 7-dihydroxy-7H-benzo [ c ] -fluorene are used as raw materials, p-toluenesulfonic acid is used as a catalyst, a mobile phase is xylene, the mass fraction of the mobile phase containing reaction raw materials is 40%, and the mass fraction of the mobile phase containing the catalyst is 5 per thousand. 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 to the catalyst of 1:1:0.01 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, and reacting for 2.5 hours at 70 ℃ to obtain a solution containing the target photochromic dye, wherein the reaction formula 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 247-251 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 3, 3-bis (4-methoxyphenyl) -6, 7-dimethoxy-13-methyl-13-hydroxy-indeno [1,2-f ] naphtho [1,2-b ] pyran.
Example 9
1- (4- (2- (2-hydroxyethoxy) ethoxy) phenyl) -1- (4-methoxyphenyl) -2-propyne-1-ol and 2, 3-dimethoxy-7, 7-dimethyl-9-trifluoromethyl-5-hydroxy-7H-benzo [ c ] -fluorene are used as raw materials, p-toluenesulfonic acid is used as a catalyst, a mobile phase is xylene, the mass fraction of the mobile phase containing reaction raw materials is 15%, and the mass fraction of the mobile phase containing the catalyst is 1 per thousand. And (3) pre-adjusting the temperature of the mobile phase system to 50 ℃, regulating and controlling the speed according to the molar ratio of the reactant raw materials to the catalyst of 1:1:0.01 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, and reacting for 4 hours at 50 ℃ to obtain a solution containing the target optically variable dye, wherein the reaction formula is shown as follows. The solution is concentrated, recrystallized, decolorized and dried to obtain a gray green powder product. The melting point of the product is 96-98 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 3- (4- (2- (2-hydroxyethoxy) ethoxy) phenyl) -3- (4-methoxyphenyl) -6, 7-dimethoxy-13, 13-dimethyl-11-trifluoromethyl-indeno [1,2-f ] naphtho [1,2-b ] pyran.
Example 10
1, 1-di (4-methoxyphenyl) -2-propyne-1-alcohol and 7-butoxy-3-methoxy-7-methyl-5-hydroxy-7H-benzo [ c ] -fluorene are used as raw materials, dodecylbenzene sulfonic acid is used as a catalyst, a mobile phase is tetrahydrofuran, the mass fraction of the mobile phase containing reaction raw materials is 30%, and the mass fraction of the mobile phase containing the catalyst is 3 per thousand. And (3) pre-adjusting the temperature of the mobile phase system to 110 ℃, regulating and controlling the speed according to the molar ratio of the reactant raw materials to the catalyst of 1:1:0.01 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, and reacting for 0.5h at 110 ℃ to obtain a solution containing the target photochromic dye, wherein the reaction formula is shown as follows. The solution was concentrated, recrystallized, decolorized and dried to give a pale green powder. The melting point of the product is 230-233 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 13-butoxy-6-methoxy-3, 3-di (4-methoxyphenyl) -13-methyl-indeno [1,2-f ] naphtho [1,2-b ] pyran.
Example 11
1, 1-bis (4- (2-methoxyethoxy) phenyl) -2-propyne-1-ol and 3, 7-dimethyl-5, 7-dihydroxy-7H-benzo [ c ] -fluorene are used as raw materials, dodecylbenzene sulfonic acid is used as a catalyst, a mobile phase is tetrahydrofuran, the mass fraction of the mobile phase containing reaction raw materials is 40%, and the mass fraction of the mobile phase containing the catalyst is 5 per mill. And (2) 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 1:1:0.01 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, and reacting for 1h at 60 ℃ to obtain a solution containing the target optically variable dye, wherein the reaction formula 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 164-166 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 3, 3-bis (4-methoxyphenyl) -6, 7-dimethoxy-13, 13-dimethyl-indeno [1,2-f ] naphtho [1,2-b ] pyran.
Example 12
1, 1-bis (4-methoxyphenyl) -2-propyne-1-ol and 7-butoxy-2, 3-dimethoxy-7-methyl-5-hydroxy-7H-benzo [ c ] -fluorene are used as raw materials, dodecylbenzene sulfonic acid is used as a catalyst, a mobile phase is xylene, the mass fraction of the mobile phase containing reaction raw materials is 40%, and the mass fraction of the mobile phase containing the catalyst is 5 per thousand. And (2) 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 1:1:0.01 by a constant flow pump, respectively injecting the reactant raw materials and the catalyst into a microchannel reactor for mixing, and reacting for 1h at 60 ℃ to obtain a solution containing the target optically variable dye, wherein the reaction formula is shown as follows. The solution is concentrated, recrystallized, decolored and dried to obtain a light green powder product. The melting point of the product is 182-184 ℃, and the nuclear magnetic resonance spectrum shows that the obtained product has a structure conforming to 13-butoxy-6, 7-dimethoxy-3, 3-di (4-methoxyphenyl) -13-methyl-indeno [1,2-f ] naphtho [1,2-b ] pyran.
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 (8)
1. A method for synthesizing naphthopyran photochromic dye by using a microchannel reactor is characterized by comprising the following steps: respectively dissolving or uniformly dispersing a compound A and a compound B as reaction raw materials and a catalyst in a mobile phase to prepare corresponding mobile phase solutions, adjusting the system temperature of the mobile phase solutions to the reaction temperature through a pre-reaction system, respectively injecting the mobile phase solutions into a microchannel reactor through a constant flow pump to perform mixing temperature control reaction to obtain a solution containing a 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.
2. The method of claim 1, wherein compound a has the formula:
wherein R1, R2, R3 and R4 may be the same OR different and each independently represents any one of hydrogen, halogen, C1-C8 alkyl, C1-C6 alkoxy, halo (C1-C8) alkane, hydroxyl, C1-C6 alkoxy (C1-C8) alkyl OR-OR, wherein R is C1-C6 alkoxy (C1-C8) alkyl, and the halogen OR halo group is fluorine, chlorine OR bromine.
3. The method of claim 1, wherein compound B has the formula:
Wherein, R5, R6, R7 and R8 may be the same OR different, each independently represents hydrogen, halogen, C1-C8 alkyl, C1-C6 alkoxy, halo (C1-C8) alkyl, hydroxy, C1-C6 alkoxy (C1-C8) alkyl, C1-C4 alkylcarboxyl, halo C1-C4 alkylcarboxyl, substituted OR unsubstituted phenyl, -OR 'OR-OC (O) X, wherein the substituent of phenyl is C1-C4 alkyl, C1-C4 alkoxy OR halogen, R' is C1-C6 alkoxy (C1-C8) alkyl, X is (C1-C8) alkyl OR halo (C1-C8) alkyl, the halo OR halo group is fluorine, chlorine OR bromine, and a, b, C and d are each 1,2 OR 3.
4. The method of claim 1, wherein compound B has the formula:
wherein R9, R10, R11 and R12 may be the same OR different, each independently represents hydrogen, halogen, C1-C8 alkyl, C1-C6 alkoxy, halo (C1-C8) alkane, hydroxy, C1-C6 alkoxy (C1-C8) alkyl OR-OR ", wherein R" is C1-C6 alkoxy (C1-C8) alkyl, said halogen OR halo is fluorine, chlorine OR bromine, wherein e and f are each 1,2 OR 3.
5. The method of claim 1, wherein the catalyst is at least one of p-toluenesulfonic acid, dodecylbenzenesulfonic acid;
the mobile phase is at least one of benzene, toluene, xylene, tetrahydrofuran or cyclohexane.
6. 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.
7. 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 0.5-5 h.
8. The method according to claim 1, wherein the mobile phase solution of the compound a and the compound B is a uniform dispersion with a mass fraction of 5-40%, and the mobile phase solution of the catalyst is a uniform dispersion with a mass fraction of 1% o-1%.
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