CN116535875A - Preparation method of silicon hydrogel contact lens colorant - Google Patents
Preparation method of silicon hydrogel contact lens colorant Download PDFInfo
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- CN116535875A CN116535875A CN202211107666.8A CN202211107666A CN116535875A CN 116535875 A CN116535875 A CN 116535875A CN 202211107666 A CN202211107666 A CN 202211107666A CN 116535875 A CN116535875 A CN 116535875A
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 22
- 239000003086 colorant Substances 0.000 title claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 14
- 229910052710 silicon Inorganic materials 0.000 title abstract description 14
- 239000010703 silicon Substances 0.000 title abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 22
- PAZPNGYXNBABCM-UHFFFAOYSA-N 1,4-bis(2-hydroxyethylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCO)=CC=C2NCCO PAZPNGYXNBABCM-UHFFFAOYSA-N 0.000 claims abstract description 17
- LDTTXRCXIMXYEV-UHFFFAOYSA-N [4-(4-methylphenyl)sulfonyloxy-9,10-dioxoanthracen-1-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC(C=1C(=O)C2=CC=CC=C2C(=O)C=11)=CC=C1OS(=O)(=O)C1=CC=C(C)C=C1 LDTTXRCXIMXYEV-UHFFFAOYSA-N 0.000 claims abstract description 11
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000012043 crude product Substances 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000001953 recrystallisation Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000012044 organic layer Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- SUSSMAWGVJTGOM-UHFFFAOYSA-N 2-[[4-[2-(2-methylprop-2-enoyloxy)ethylamino]-9,10-dioxoanthracen-1-yl]amino]ethyl 2-methylprop-2-enoate Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCOC(=O)C(C)=C)=CC=C2NCCOC(=O)C(=C)C SUSSMAWGVJTGOM-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- -1 contact lenses Substances 0.000 description 1
- 210000004087 cornea Anatomy 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
- C07C225/24—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings
- C07C225/26—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings
- C07C225/32—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings of condensed quinone ring systems formed by at least three rings
- C07C225/34—Amino anthraquinones
-
- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/02—Lenses; Lens systems ; Methods of designing lenses
- G02C7/04—Contact lenses for the eyes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Ophthalmology & Optometry (AREA)
- Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
Abstract
The invention relates to a preparation method of a silicon hydrogel contact lens colorant, belonging to the technical field of fine chemistry and new materials. The colorant is suitable for being applied to vision optical materials such as silicon hydrogel contact lenses, artificial lenses and the like and high-end medical appliance products. The invention takes 1, 4-bis (p-toluenesulfonyloxy) -9, 10-anthraquinone as a raw material, reacts with 2-amino ethanol to obtain 1, 4-bis ((2-hydroxyethyl) amino) -9, 10-anthraquinone, and then reacts with methacryloyl chloride to obtain a target product. The preparation method has the advantages of simple preparation steps, easily obtained raw materials, mild reaction conditions, easy control and higher product yield, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the fields of fine chemistry and new materials, and particularly relates to a preparation method of a silicon hydrogel contact lens colorant, which is very suitable for application of visual optical materials such as contact lenses, silicon hydrogel contact lenses, artificial lenses and the like and high-end medical instrument products.
Background
Silicone hydrogels are novel contact lens materials that possess both the high oxygen permeability of silicone materials and the softness and hydrophilicity of hydrogel materials. The silicon hydrogel contact lens is provided with a water channel and a double oxygen permeation channel of the silicon channel, the oxygen permeation performance is 6-10 times higher than that of common hydrogel, more oxygen can directly reach the cornea, and the wearing is more comfortable.
The prepared colorant for the silicon hydrogel contact lens has the chemical name of 1, 4-bis [ (2-methacryloyloxyethyl) amino ] -9, 10-anthraquinone and CAS (CAS) 109561-07-1, and is a few colorants approved by the FDA in the United states for application in contact lenses. The 1, 4-bis [ (2-methacryloyloxyethyl) amino ] -9, 10-anthraquinone can be widely applied to the field of visual optical materials, can be used as a colorant for artificial lenses and contact lenses, and has the advantages of low usage amount, good coloring performance, long-term stability, difficult fading and the like. Because the compound has two methacrylate functional groups, dye molecules can be covalently bound into a high-molecular base material with high efficiency, and high dye loading can be realized.
At present, no report is made on the preparation method of 1, 4-bis [ (2-methacryloyloxyethyl) amino ] -9, 10-anthraquinone. Thus, there is a need to develop a simple, easy to handle process for preparing 1, 4-bis [ (2-methacryloyloxyethyl) amino ] -9, 10-anthraquinone.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a silicone hydrogel contact lens colorant. The method has the advantages of simple steps, easily obtained raw materials, low reaction condition and high yield, and is suitable for large-scale industrial production.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing a silicone hydrogel contact lens colorant, the structural formula of the product being as follows:
a method of preparing a silicone hydrogel contact lens colorant comprising the steps of:
step 1: mixing 2-amino ethanol and 1, 4-bis (p-toluenesulfonyloxy) -9, 10-anthraquinone according to a certain proportion, adding a solvent for dissolution, heating to 50-100 ℃ under the protection of nitrogen, and reacting for 3-8h. After the reaction, the solvent was distilled off, diluted with water, extracted 3 times with ethyl acetate, and the organic layers were combined. Concentrating under reduced pressure to obtain crude product, and recrystallizing with methanol to obtain 1, 4-bis ((2-hydroxyethyl) amino) -9, 10-anthraquinone;
step 2: 1, 4-bis ((2-hydroxyethyl) amino) -9, 10-anthraquinone is dissolved in methylene dichloride, triethylamine is added as an acid binding agent, the temperature is reduced to 0 ℃, methacryloyl chloride is started to be added dropwise, and the reaction temperature is controlled to be 0-10 ℃. After the dripping is finished, the reaction is continued for 2 to 4 hours after the temperature is raised to the room temperature, and then the crude product is obtained through filtration, water washing and concentration. And adding a solvent into the crude product for recrystallization to obtain a target product.
Preferably, the solvent used in the step 1 is tetrahydrofuran, N-dimethylformamide or 1, 4-dioxane.
Preferably, in the step 1, the molar ratio of the 1, 4-bis (p-toluenesulfonyloxy) -9, 10-anthraquinone to the 2-aminoethanol is 1:2.0-6.0.
Preferably, in the step 2, the molar ratio of 1, 4-bis ((2-hydroxyethyl) amino) -9, 10-anthraquinone, methacryloyl chloride and triethylamine is 1:2.0-2.5:2.0-2.5.
Preferably, the recrystallization solvent used in the step 2 is methanol, ethanol or tetrahydrofuran.
The invention has the beneficial effects of. The preparation method disclosed by the invention has the advantages of easily available raw materials, simplicity in operation, fewer reaction impurities, easiness in purification of products and higher total yield. In addition, the invention selects 1, 4-bis (p-toluenesulfonyloxy) -9, 10-anthraquinone as a raw material to react with 2-amino ethanol, the substrate has higher reactivity, mild reaction conditions and fewer side reactions, and is beneficial to improving the reaction yield.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of 1, 4-bis [ (2-methacryloyloxyethyl) amino ] -9, 10-anthraquinone, which is the product obtained in example 1 of the present invention.
FIG. 2 shows the chemical reaction scheme of example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1
The embodiment provides a preparation method of a silicon hydrogel contact lens colorant, which specifically comprises the following steps:
step 1: 48.9g of 2-aminoethanol was weighed and mixed with 109.7g of 1, 4-bis (p-toluenesulfonyloxy) -9, 10-anthraquinone, 300ml of tetrahydrofuran was added thereto, and the mixture was heated to 55℃under nitrogen protection and reacted for 7 hours. After the reaction, the solvent was distilled off, diluted with water, extracted 3 times with ethyl acetate, and the organic layers were combined. Concentrating under reduced pressure to obtain a crude product, recrystallizing with methanol, filtering, and oven drying to obtain 61.2g of 1, 4-bis ((2-hydroxyethyl) amino) -9, 10-anthraquinone;
step 2: 61.2g of 1, 4-bis ((2-hydroxyethyl) amino) -9, 10-anthraquinone obtained in the step 1 is dissolved in 500ml of dichloromethane, 43.6g of triethylamine is added as an acid binding agent, the temperature is reduced to 0 ℃, 45.1g of methacryloyl chloride is started to be added dropwise, and the reaction temperature is controlled to be 0-10 ℃. After the completion of the dropwise addition, the reaction was continued at room temperature for 2 hours. Filtering after the reaction is finished, washing with water to be neutral, and concentrating under reduced pressure to obtain a crude product. Tetrahydrofuran is added into the crude product for recrystallization, filtration and drying are carried out, 78.7g of target product is obtained, and the total yield is 85.1%.
Example 2
The embodiment provides a preparation method of a silicon hydrogel contact lens colorant, which specifically comprises the following steps:
step 1: 36.7g of 2-aminoethanol and 109.7g of 1, 4-bis (p-toluenesulfonyloxy) -9, 10-anthraquinone were weighed and mixed, 200ml of N, N-dimethylformamide was added thereto, and the temperature was raised to 100℃under nitrogen protection for reaction for 3 hours. After the reaction, the solvent was distilled off, diluted with water, extracted 3 times with ethyl acetate, and the organic layers were combined. Concentrating under reduced pressure to obtain a crude product, recrystallizing with methanol, filtering, and oven drying to obtain 57.9g of 1, 4-bis ((2-hydroxyethyl) amino) -9, 10-anthraquinone;
step 2: 57.9g of 1, 4-bis ((2-hydroxyethyl) amino) -9, 10-anthraquinone obtained in the step 1 is dissolved in 500ml of dichloromethane, 41.3g of triethylamine is added as an acid binding agent, the temperature is reduced to 0 ℃, 42.7g of methacryloyl chloride is started to be added dropwise, and the reaction temperature is controlled to be 0-10 ℃. After the completion of the dropwise addition, the reaction was continued at room temperature for 2 hours. Filtering after the reaction is finished, washing with water to be neutral, and concentrating under reduced pressure to obtain a crude product. Methanol is added into the crude product for recrystallization, filtration and drying are carried out, 75.6g of target product is obtained, and the total yield is 81.7%.
Example 3
The embodiment provides a preparation method of a silicon hydrogel contact lens colorant, which specifically comprises the following steps:
step 1: 109.9g of 2-aminoethanol were weighed and mixed with 164.6g of 1, 4-bis (p-toluenesulfonyloxy) -9, 10-anthraquinone, 400ml of tetrahydrofuran was added thereto, and the mixture was heated to 50℃under nitrogen protection and reacted for 6 hours. After the reaction, the solvent was distilled off, diluted with water, extracted 3 times with ethyl acetate, and the organic layers were combined. Concentrating under reduced pressure to obtain a crude product, recrystallizing with methanol, filtering, and drying to obtain 91.2g of 1, 4-bis ((2-hydroxyethyl) amino) -9, 10-anthraquinone;
step 2: 91.2g of 1, 4-bis ((2-hydroxyethyl) amino) -9, 10-anthraquinone obtained in the step 1 is dissolved in 700ml of dichloromethane, 67.9g of triethylamine is added as an acid binding agent, the temperature is reduced to 0 ℃, 70.1g of methacryloyl chloride is started to be added dropwise, and the reaction temperature is controlled to be 0-10 ℃. After the completion of the dropwise addition, the reaction was continued at room temperature for 3 hours. Filtering after the reaction is finished, washing with water to be neutral, and concentrating under reduced pressure to obtain a crude product. Tetrahydrofuran is added into the crude product for recrystallization, filtration and drying are carried out, thus obtaining 118.7g of target product with the total yield of 85.6 percent.
Example 4
The embodiment provides a preparation method of a silicon hydrogel contact lens colorant, which specifically comprises the following steps:
step 1: 122.2g of 2-aminoethanol was weighed and mixed with 274.3g of 1, 4-bis (p-toluenesulfonyloxy) -9, 10-anthraquinone, 600ml of 1, 4-dioxane was added thereto, and the temperature was raised to 65℃under nitrogen protection for reaction for 6 hours. After the reaction, the solvent was distilled off, diluted with water, extracted 3 times with ethyl acetate, and the organic layers were combined. Concentrating under reduced pressure to obtain a crude product, recrystallizing with methanol, filtering, and oven drying to obtain 148.8g of 1, 4-bis ((2-hydroxyethyl) amino) -9, 10-anthraquinone;
step 2: 148.8g of 1, 4-bis ((2-hydroxyethyl) amino) -9, 10-anthraquinone obtained in the step 1 is dissolved in 1L of dichloromethane, 106.1g of triethylamine is added as an acid binding agent, the temperature is reduced to 0 ℃, 104.8g of methacryloyl chloride is started to be added dropwise, and the reaction temperature is controlled to be 0-10 ℃. After the completion of the dropwise addition, the reaction was continued at room temperature for 4 hours. Filtering after the reaction is finished, washing with water to be neutral, and concentrating under reduced pressure to obtain a crude product. Ethanol is added into the crude product for recrystallization, filtration and drying are carried out, and 191.6g of target product is obtained, and the total yield is 82.9%.
Example 5
The embodiment provides a preparation method of a silicon hydrogel contact lens colorant, which specifically comprises the following steps:
step 1: 80.6g of 2-aminoethanol are weighed and mixed with 329.1g of 1, 4-bis (p-toluenesulfonyloxy) -9, 10-anthraquinone, 600ml of N, N-dimethylformamide are added, and the temperature is raised to 80 ℃ for reaction for 5 hours under the protection of nitrogen. After the reaction, the solvent was distilled off, diluted with water, extracted 3 times with ethyl acetate, and the organic layers were combined. Concentrating under reduced pressure to obtain crude product, recrystallizing with methanol, filtering, and oven drying to obtain 168.6g of 1, 4-bis ((2-hydroxyethyl) amino) -9, 10-anthraquinone;
step 2: 168.6g of 1, 4-bis ((2-hydroxyethyl) amino) -9, 10-anthraquinone obtained in the step 1 is dissolved in 1L of dichloromethane, 125.5g of triethylamine is added as an acid binding agent, the temperature is reduced to 0 ℃, 129.6g of methacryloyl chloride is started to be added dropwise, and the reaction temperature is controlled to be 0-10 ℃. After the completion of the dropwise addition, the reaction was continued at room temperature for 4 hours. Filtering after the reaction is finished, washing with water to be neutral, and concentrating under reduced pressure to obtain a crude product. Methanol is added into the crude product for recrystallization, filtration and drying are carried out, 220.1g of target product is obtained, and the total yield is 79.3%.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (6)
1. A method for preparing a silicone hydrogel contact lens colorant, wherein the structural formula of the target product is as follows:
。
2. a method of preparing a silicone hydrogel contact lens colorant comprising the steps of:
step 1: mixing 2-aminoethanol and 1, 4-bis (p-toluenesulfonyloxy) -9, 10-anthraquinone according to a certain proportion, adding a solvent for dissolution, heating to 50-100 ℃ under the protection of nitrogen, and reacting for 3-8h; evaporating the solvent after the reaction is finished, adding water for dilution, adding ethyl acetate for extraction for 3 times, and combining the organic layers; concentrating under reduced pressure to obtain crude product, and recrystallizing with methanol to obtain 1, 4-bis ((2-hydroxyethyl) amino) -9, 10-anthraquinone;
step 2: dissolving 1, 4-bis ((2-hydroxyethyl) amino) -9, 10-anthraquinone in dichloromethane, adding triethylamine as an acid binding agent, cooling to 0 ℃, beginning to dropwise add methacryloyl chloride, and controlling the reaction temperature to 0-10 ℃; after the dripping is finished, the reaction is continued for 2 to 4 hours after the temperature is raised to the room temperature, and then the crude product is obtained through filtration, water washing and concentration; and adding a solvent into the crude product for recrystallization to obtain a target product.
3. The method of claim 2, wherein the solvent used in step 1 is tetrahydrofuran, N-dimethylformamide or 1, 4-dioxane.
4. The method of claim 2, wherein the molar ratio of 1, 4-bis (p-toluenesulfonyloxy) -9, 10-anthraquinone to 2-aminoethanol in step 1 is 1:2.0-6.0.
5. The method for preparing a silicone hydrogel contact lens colorant of claim 2, wherein the molar ratio of 1, 4-bis ((2-hydroxyethyl) amino) -9, 10-anthraquinone, methacryloyl chloride, and triethylamine in step 2 is 1:2.0-2.5:2.0-2.5.
6. The method of claim 2, wherein the recrystallization solvent used in step 2 is methanol, ethanol or tetrahydrofuran.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013079055A1 (en) * | 2011-11-30 | 2013-06-06 | S&V Technologies Ag | Polymerisable dyes and compositions thereof for ophthalmological applications |
| CN104011110A (en) * | 2011-02-28 | 2014-08-27 | 库柏维景国际控股公司 | Dimensionally stable silicone hydrogel contact lenses |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104011110A (en) * | 2011-02-28 | 2014-08-27 | 库柏维景国际控股公司 | Dimensionally stable silicone hydrogel contact lenses |
| WO2013079055A1 (en) * | 2011-11-30 | 2013-06-06 | S&V Technologies Ag | Polymerisable dyes and compositions thereof for ophthalmological applications |
Non-Patent Citations (1)
| Title |
|---|
| 甘莹 等: "双取代蒽醌-多胺缀合物的合成及其抗肿瘤细胞增殖活性研究", 中国药物化学杂志, vol. 24, no. 5, 31 October 2014 (2014-10-31), pages 358 - 363 * |
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