CN115215874A - Tetra-aryl porphyrin compound containing olefine acid ester and application thereof - Google Patents
Tetra-aryl porphyrin compound containing olefine acid ester and application thereof Download PDFInfo
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Abstract
The invention discloses a tetraaryl porphyrin compound containing olefine acid ester, which has excellent high-energy short-wave blue light absorption characteristic and thermal stability, can be used as a cross-linking agent due to the fact that the tail end of the structure contains four C = C bonds, can be polymerized with other monomers through chemical bonding to form a space network structure, and has the advantages of effectively cross-linking polymer materials and enhancing the stability of the materials. The macromolecular material prepared by only adding 0.05 percent of the compound can effectively filter 385-445 nm harmful blue light (the average transmittance is less than 60 percent), particularly has the average transmittance of less than 50 percent for 400-420 nm high-energy short-wave blue light, does not affect 446-505 nm beneficial blue light (the transmittance is close to 100 percent), does not show yellow, does not cause color display distortion, and can achieve better harmful blue light filtering effect under the condition of extremely small addition amount. The blue light filter can be used for selectively filtering blue light with different wave bands and different intensities in different fields by adjusting the addition amount of the blue light filter.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a tetraaryl porphyrin compound containing olefine acid ester and application thereof.
Background
Blue light refers to light with a waveband ranging from 385 to 505nm (Arch Ophthalmol,2005, 123, 550-555), and is further divided into harmful blue light (385 to 445 nm) and beneficial blue light (446 to 505 nm). Electronic products such as natural light, computers, televisions, mobile phones, LED lamps, etc. can emit harmful blue light with different doses, and a series of symptoms such as eye soreness, dry itching, asthenopia, even headache, emotional dysphoria, etc. can be caused by long-term contact, which is called Video Display Terminal (VDT) syndrome (surfey of Ophthalmology,2005, 50, 253-262). Among them, high-energy short-wave blue light of 400-420 nm causes 80% of damage, and is the main band affecting human health (Cosmetics & Toiletries,2011, 126, 186, 188-194, materials Chemistry and Physics,2018, 216, 365-371 and Acta optosalmol Scad, 2006, 84, 4-15). In order to prevent harmful blue light from continuously damaging human eyes, products such as blue light prevention goggles, blue light prevention films and the like are developed in succession, but the quality is uneven, and the blue light prevention effect is also greatly different. Commercially available blue light-proof products mainly adopt a broad-spectrum shielding method, harmful blue light is filtered, beneficial blue light is blocked (beneficial to adjusting human body physiological rhythm and improving sleep), shielding strength is uneven, and the non-selective shielding easily causes color vision deviation and can influence normal circadian rhythm of human beings in serious cases (Neurochemical Research,2015, 40, 284-292).
Porphyrin is a general name of homologs and derivatives of porphin with substituent at outer ring, is a large conjugated system bridged by 4 pyrrole rings and 4 methines, has good biocompatibility and high chemical stability, and is widely present in heme and chlorophyllVitamin, vitamin B 12 And the like in natural life (Chemical Society Reviews,1995, 24, 19-33). The compound has good light absorption characteristics (ACS Applied Materials)&Interfaces,2016,8, 27438-27443), by changing the substituent type on the ring, the absorption spectrum can be red-shifted and the peak can be broadened. Scholars at home and abroad prepare some blue light-proof materials by utilizing the good biocompatibility and excellent light absorption performance of porphyrin compounds. For example: the advanced science corporation reported a patent for Cu-porphyrin dye compounds for selective blue light filtration (CN 201580036787. X) with an average transmittance of at least 80% between 460 and 700nm and an average transmittance of less than 75% between 400 and 460 nm. The compound is placed in the optical system in a coating form, harmful blue light is filtered, and meanwhile, part of beneficial blue light is blocked. The high performance optics company has reported a patent for selective photoinhibition of ophthalmic systems (CN 200780029228.1), which uses porphyrin as a dye, and can selectively absorb at least 5% of light with a wavelength range of 400-460 nm, while visible light has an average transmittance of at least 80%. However, the system has a weak effect of filtering harmful blue light, and the transmittance of the system to visible light is not ideal.
Although some blue light absorbing materials have been prepared using the light absorbing properties of porphyrins, the following problems remain: (1) Part of the material cuts the blue light excessively, so that harmful blue light is blocked, and part of beneficial blue light is also blocked, thereby not only causing display distortion of object color, but also being beneficial to absorption of beneficial blue light by human body; (2) Under the condition of low porphyrin addition amount, the harmful blue light filtering effect of part of materials is weaker, but with the increase of the porphyrin addition amount, the color of the materials is deepened, the visible light transmittance is reduced, and the hue, saturation and brightness of a picture in the process of viewing an object are influenced; (3) Most porphyrins in the material are coated or dissolved, but are not chemically bonded, and can be separated out after long-term use, so that the application in organisms is not facilitated. Therefore, it is important to find a blue light-proof material which has biological safety and display effect.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing a tetraaryl porphyrin compound containing olefine acid ester, which can effectively block harmful blue light under a very low addition amount, and provides application of the tetraaryl porphyrin compound in preparing a high polymer material for selectively filtering harmful blue light, particularly 400-420 nm high-energy short-wave blue light, and application in preparing contact lenses.
The technical scheme is as follows: in order to solve the technical problems, the invention provides a tetraarylporphyrin compound containing alkenoic acid ester, which has a structure shown in a general formula I:
wherein: x1, X2, X3 and X4 are respectively and independently selected from one of hydrogen, halogen, cyano-group, nitro-group, alkyl, halogenated alkyl and alkyl carbonyl; the halogen is fluorine, chlorine, bromine or iodine; the halogenation in the halogenated alkyl is fluoro, chloro, bromo or iodo; r is selected from H or alkyl; n =1 or 2 or 3 or 4.
Wherein R is H or methyl or ethyl.
Wherein, X1, X2, X3 and X4 are one of hydrogen, methyl, ethyl, fluorine, chlorine, trifluoromethyl, isopropyl or nitro.
Wherein the compound has a structural formula:
the invention also comprises the application of the tetraaryl porphyrin compound containing the olefine acid ester in preparing a high polymer material for filtering high-energy short-wave blue light with the wavelength of 400-420 nm.
The invention also discloses an application of the tetraaryl porphyrin compound containing the alkenoic acid ester in preparing contact lenses.
The invention provides a high-energy short-wave blue light resistant contact lens which is prepared by adding tetraaryl porphyrin compounds containing olefine acid ester into hydrogel lens raw materials or non-hydrogel lens raw materials. The hydrogel lens raw material comprises hydrophilic monomers such as hydroxyethyl methacrylate, N-vinyl pyrrolidone, methacrylic acid, glycidyl methacrylate, polyvinyl alcohol and the like, organic silicon monomers such as methacryloxypropyl tris (trimethylsiloxy) silane, gamma-aminopropyltriethoxysilane, 3- (methacryloxy) propyltrimethoxysilane, 3- (3-methacryloxy-2-hydroxypropyl) propyl bis (trimethylsiloxane) methyl silane, crosslinking agents, initiators and the like, and monomers of commercially available contact lens materials (such as Polymaccon, hioxifilcon, mafilcon, hefilcon, nesoffilcon, omafilcon, droxifilcon, delafilcon, etafilcon, balafilcon, delefilcon, lotrafilcon, entracon, seafilcon, senefilcon, narafilcon, somocon and the like). The non-hydrogel lens raw material comprises monomers such as methyl methacrylate, cellulose acetate butyrate, siloxane methacrylate, fluorinated siloxane methacrylate, olefin siloxane and the like.
Has the advantages that: the invention has the following advantages:
1. the tetraaryl porphyrin compound containing the olefine acid ester is a new compound, and compared with the existing similar structure (such as tetra [ (4-hydroxy) phenyl ] porphyrin, see the compound II-1 in the embodiment 1), the tetraaryl porphyrin compound containing the olefine acid ester has more excellent high-energy short-wave blue light absorption characteristic and thermal stability, the maximum absorption wavelength is near 420nm, the absorption spectrum is wider, and the initial decomposition temperature is near 200 ℃.
2. The compound is prepared by taking cheap and easily-obtained pyrrole and substituted methoxyl aromatic aldehyde as raw materials through only 3 steps of reaction, and the compound is simple in synthetic method, free of fussy post-treatment and easy to industrialize.
3. The compound has the structure tail end containing four C = C bonds, can be polymerized with other monomers through chemical bonding by photo initiation or thermal initiation to form a space network structure, has the functions of effectively crosslinking a polymer material and enhancing the stability of the material, and has the advantages of simple polymerization method, no need of harsh conditions such as nitrogen protection and the like.
4. As the structure of the compound is introduced with ester groups with different alkyl chain lengths, compared with the existing similar structure (Dyes and Pigments,2019, 161, 155-161), the compound has the advantages that the solubility in ethyl acetate is increased along with the growth of an alkyl chain, and the compound with the alkyl chain length is dissolved more by using a solvent with the same volume, thereby indicating that the compound has better fat solubility. In addition, absorption spectrum tests show that the compound with the alkyl chain length has a better high-energy short-wave blue light filtering effect, and show that the steric hindrance is reduced and the polymerization degree is increased during polymerization along with the increase of the alkyl chain.
5. The high polymer material and the contact lens prepared by only adding 0.05 percent of the compound can effectively filter 385-445 nm harmful blue light (the average transmittance is lower than 60 percent), particularly have the average transmittance of lower than 50 percent for 400-420 nm high-energy short-wave blue light, do not influence the transmission of 446-505 nm beneficial blue light (the transmittance is close to 100 percent), and have less addition amount, better filtering effect of harmful blue light and higher transmittance of beneficial blue light and visible light compared with the currently reported blue light preventing material.
6. The high molecular material and the contact lens prepared by adding the compound do not show yellow, do not cause color display distortion, and do not influence the hue, saturation and brightness of pictures when objects are viewed. Because the chemical bonding mode is adopted, but not the coating or dissolving mode, the precipitation problem can not occur after long-term use, and the method is expected to be applied to organisms.
7. With the increase of the addition amount of the compound, the blue light absorption effect is enhanced, and the compound can be used for selectively filtering blue light with different wave bands and different intensities in different fields by adjusting the addition amount.
Drawings
FIG. 1 Hydrogen spectrum of Compound II-1 of example 1.
FIG. 2 Hydrogen spectrum of Compound I-1 in example 2.
FIG. 3 Hydrogen spectrum of Compound I-2 in example 3.
Figure 4 image of hydrogel lens prepared in example 26.
Figure 5 image of hydrogel lens prepared in example 27.
Figure 6 is a photograph of a hydrogel lens prepared in comparative example 3.
Figure 7 picture of silicone hydrogel lens prepared in example 28.
FIG. 8 is a photograph of a silicone hydrogel lens prepared in example 29.
Figure 9 is a picture of a silicone hydrogel lens prepared in comparative example 4.
FIG. 10 DSC analysis of Compound I-1 of example 2.
FIG. 11 DSC analysis of compound I-2 of example 3.
FIG. 12 comparative infrared plots of compound I-1 of example 2 at different temperatures.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to specific examples.
EXAMPLE 1 Synthesis of tetrakis [ (4-hydroxy) phenyl ] porphyrin (Compound II-1)
Synthetic route of tetrakis [ (4-hydroxy) phenyl ] porphyrin (compound II-1):
500mL of propionic acid solution, 20.8mL of pyrrole and 36.5mL of 4-methoxybenzaldehyde were sequentially added to a three-necked round-bottomed flask, and a reflux reaction was carried out for 0.5h. Cooling to room temperature, filtering, and recrystallizing the crude product with ethyl acetate/petroleum ether to obtain purple solid IV-1. Mixing IV-1 with BBr 3 Stirring in dichloromethane at room temperature to prepare purple solid II-1. Nuclear magnetic data ( 1 HNMR,400MHz, internal standard TMS, solvent DMSO-d 6 ) The following were used: δ ppm 9.99 (s, 4H), 8.88 (s, 8H), 8.01 (d, J =6.3hz, 8h), 7.21 (d, J =6.2hz, 8h), -2.87 (s, 2H). (the hydrogen spectrum is shown in FIG. 1)
EXAMPLE 2 Synthesis of tetrakis [ (4-butenyloxy) phenyl ] porphyrin (Compound I-1)
Synthetic route of tetra [ (4-butenyloxy) phenyl ] porphyrin (compound I-1):
at the temperature of 0 ℃, 10.32g of crotonic acid and 24.72g of DCC are dissolved in 250mL of dichloromethane, stirred and reacted for 0.5h, then 20.4g of compound II-1 and 1.2g of DMAP are added, stirring is continued for 1h, then the mixture is heated to room temperature and stirred for 24h, concentrated, and separated and purified by column chromatography to obtain purple solid I-1. Nuclear magnetic data ( 1 H NMR,400MHz, internal standard TMS, solvent CDCl 3 ) The following were used: δ ppm 8.90 (d, J =7.2hz, 8h), 8.23 (d, J =8.4hz, 8h), 7.55 (d, J =8.4hz, 8h), 6.27-6.16 (m, 4H), 5.47-5.38 (m, 8H), 3.57 (d, J =6.9hz, 8h), -2.81 (s, 2H). (the hydrogen spectrum is shown in FIG. 2)
EXAMPLE 3 Synthesis of tetrakis [ (4-pentenoyloxy) phenyl ] porphyrin (Compound I-2)
Synthetic route of tetrakis [ (4-pentenoyloxy) phenyl ] porphyrin (compound I-2):
dissolving 12.03g of pentenoic acid and 24.72g of DCC in 250mL of dichloromethane at 0 ℃, stirring for reaction for 0.5h, adding 20.4g of compound II-1 and 1.2g of DMAP, continuing stirring for 1h, raising the temperature to 40 ℃, stirring for 12h, concentrating, and performing column chromatography separation and purification to obtain a purple solid I-2. Nuclear magnetic data ( 1 H NMR,400MHz, internal standard TMS, solvent CDCl 3 ) The following were used: δ ppm 8.89 (d, J =7.2hz, 8h), 8.27 (d, J =8.4hz, 8h), 7.60 (d, J =8.4hz, 8h), 6.10-6.00 (m, 4H), 5.31-5.16 (m, 8H), 2.91 (t, J =7.2hz, 8h), 2.62-2.56 (m, 8H), -2.91 (s, 2H). (the hydrogen spectrum is shown in FIG. 3)
EXAMPLE 4 Synthesis of tetrakis [ (4-hexenoyloxy) phenyl ] porphyrin (Compound I-3)
Synthetic route of tetrakis [ (4-hexenoyloxy) phenyl ] porphyrin (compound I-3):
dissolving 13.70g of hexenoic acid and 24.72g of DCC in 250mL of dichloromethane at the temperature of 0 ℃, stirring for reacting for 0.5h, adding 20.4g of compound II-1 and 1.2g of DMAP, continuing stirring for 1h, raising the temperature to 40 ℃, stirring for 12h, concentrating, and separating and purifying by column chromatography to obtain a purple solid I-3. The elemental analysis data are as follows: calculated values w (C) =76.82%, w (H) =5.88%, w (N) =5.27%; experimental values w (C) =76.55%, w (H) =5.86%, w (N) =5.30%.
EXAMPLE 5 Synthesis of tetrakis [ (4-methylbutenoyloxy) phenyl ] porphyrin (Compound I-4)
Synthetic route of tetrakis [ (4-methylbutenoyloxy) phenyl ] porphyrin (compound I-4):
dissolving 12.01g of methyl butenoic acid and 24.72g of DCC in 250mL of dichloromethane at 0 ℃, stirring for reacting for 0.5h, then adding 20.4g of compound II-1 and 1.2g of DMAP, continuing stirring for 1h, raising the temperature to room temperature, stirring for 24h, concentrating, and performing column chromatography separation and purification to obtain a purple solid I-4. The elemental analysis data are as follows: calculated values w (C) =76.32%, w (H) =5.40%, w (N) =5.56%; experimental values w (C) =76.59%, w (H) =5.38%, w (N) =5.53%.
EXAMPLE 6 Synthesis of tetrakis [ (4-methylpentenoyloxy) phenyl ] porphyrin (Compound I-5)
Synthetic route of tetrakis [ (4-methylpentenenoyloxy) phenyl ] porphyrin (compound I-5):
dissolving 13.70g of methylpentenoic acid and 24.72g of DCC in 250mL of dichloromethane at 0 ℃, stirring for reaction for 0.5h, then adding 20.4g of compound II-1 and 1.2g of DMAP, continuing stirring for 1h, raising the temperature to room temperature, stirring for 24h, concentrating, and performing column chromatography separation and purification to obtain a purple solid I-5. The elemental analysis data are as follows: calculated values w (C) =76.82%, w (H) =5.88%, w (N) =5.27%; experimental values w (C) =76.59%, w (H) =5.85%, w (N) =5.31%.
EXAMPLE 7 Synthesis of tetrakis [ (4-methylhexenoyloxy) phenyl ] porphyrin (Compound I-6)
Synthetic route of tetrakis [ (4-methylhexenoyloxy) phenyl ] porphyrin (compound I-6):
dissolving 15.38g of methyl hexenoic acid and 24.72g of DCC in 250mL of dichloromethane at 0 ℃, stirring for reacting for 0.5h, then adding 20.4g of compound II-1 and 1.5g of DMAP, continuing stirring for 1h, raising the temperature to 40 ℃, stirring for 12h, concentrating, and performing column chromatography separation and purification to obtain a purple solid I-6. The elemental analysis data are as follows: calculated values w (C) =77.26%, w (H) =6.30%, w (N) =5.01%; experimental values w (C) =77.55%, w (H) =6.27%, w (N) =4.98%.
EXAMPLE 8 Synthesis of tetrakis [ (4-ethylbutenoyloxy) phenyl ] porphyrin (Compound I-7)
Synthetic route of tetrakis [ (4-ethylbutenoyloxy) phenyl ] porphyrin (compound I-7):
dissolving 13.70g of ethyl crotonic acid and 24.72g of DCC in 250mL of trichloromethane at 0 ℃, stirring for reacting for 1h, then adding 20.4g of compound II-1 and 1.5g of DMAP, continuing stirring for 1.5h, raising to room temperature, stirring for 24h, concentrating, and separating and purifying by column chromatography to obtain a purple solid I-7. The elemental analysis data are as follows: calculated values w (C) =76.82%, w (H) =5.88%, w (N) =5.27%; experimental values w (C) =76.56%, w (H) =5.91%, w (N) =5.30%.
EXAMPLE 9 Synthesis of tetrakis [ (4-ethylpentenylacyloxy) phenyl ] porphyrin (Compound I-8)
Synthesis route of tetrakis [ (4-ethylpentenyloxy) phenyl ] porphyrin (Compound I-8):
dissolving 15.38g of ethyl pentenoic acid and 24.72g of DCC in 250mL of trichloromethane at 0 ℃, stirring for reaction for 1h, then adding 20.4g of compound II-1 and 1.5g of DMAP, continuing stirring for 1.5h, raising the temperature to 40 ℃, stirring for 12h, concentrating, and performing column chromatography separation and purification to obtain a purple solid I-8. The elemental analysis data are as follows: calculated values w (C) =77.26%, w (H) =6.30%, w (N) =5.01%; experimental values w (C) =77.58%, w (H) =6.27%, w (N) =4.98%.
EXAMPLE 10 Synthesis of tetrakis [ (4-chloro-3-butenyloxy) phenyl ] porphyrin (Compound I-9)
The synthetic route of tetra [ (4-chloro-3-butenyloxy) phenyl ] porphyrin (compound I-9):
tetrakis [ (4-chloro-3-hydroxy) phenyl ] porphyrin (compound II-2) was prepared by the method of synthesis of compound II-1 according to example 1. Then, 10.32g of crotonic acid and 24.72g of DCC are dissolved in 250mL of trichloromethane at the temperature of 0 ℃, stirred and reacted for 1 hour, then 24.50g of compound II-2 and 1.8g of DMAP are added, stirring is continued for 1.5 hours, then the temperature is raised to 40 ℃, stirred for 12 hours, concentrated, separated and purified by column chromatography, and the purple solid I-9 is obtained. The elemental analysis data are as follows: calculated values w (C) =66.19%, w (H) =3.89%, w (N) =5.15%; experimental values w (C) =66.45%, w (H) =3.92%, w (N) =5.12%.
EXAMPLE 11 Synthesis of tetrakis [ (2-chloro-4-pentenoyloxy) phenyl ] porphyrin (Compound I-10)
Synthetic route of tetrakis [ (2-chloro-4-pentenoyloxy) phenyl ] porphyrin (compound I-10):
tetrakis [ (2-chloro-4-hydroxy) phenyl ] porphyrin (compound II-3) was prepared by the method of synthesis of compound II-1 according to example 1. Then at 0 ℃, dissolving 12.01g of pentenoic acid and 24.72g of DCC in 250mL of trichloromethane, stirring for reaction for 1h, adding 24.50g of compound II-3 and 1.8g of DMAP, continuing stirring for 1.5h, raising the temperature to 40 ℃, stirring for 12h, concentrating, and performing column chromatography separation and purification to obtain a purple solid I-10. The elemental analysis data are as follows: calculated values w (C) =67.14%, w (H) =4.40%, w (N) =4.89%; experimental values w (C) =67.43%, w (H) =4.42%, w (N) =4.86%.
EXAMPLE 12 Synthesis of tetrakis [ (3-cyano-4-butenyloxy) phenyl ] porphyrin (Compound I-11)
Synthetic route of tetrakis [ (3-cyano-4-butenyloxy) phenyl ] porphyrin (compound I-11):
tetrakis [ (3-cyano-4-hydroxy) phenyl ] porphyrin (compound II-4) was prepared by the method of synthesis of compound II-1 according to example 1. Then 10.32g of crotonic acid and 24.72g of DCC are dissolved in 250mLN and N' -dimethylformamide at the temperature of 0 ℃, stirred and reacted for 1h, 23.36g of compound II-4 and 1.8g of DMAP are added, stirring is continued for 1.5h, then the temperature is raised to 40 ℃, stirred for 12h, concentrated and separated and purified by column chromatography, and the purple solid I-11 is obtained. The elemental analysis data are as follows: calculated values w (C) =73.13%, w (H) =4.03%, w (N) =10.66%; experimental values w (C) =69.82%, w (H) =4.05%, w (N) =10.71%.
EXAMPLE 13 Synthesis of tetrakis [ (3-nitro-4-pentenoyloxy) phenyl ] porphyrin (Compound I-12)
Synthetic route of tetrakis [ (3-nitro-4-pentenoyloxy) phenyl ] porphyrin (compound I-12):
tetrakis [ (3-nitro-4-hydroxy) phenyl ] porphyrin (compound II-5) was prepared by the method of synthesis of compound II-1 according to example 1. Then at 0 ℃, 12.01g of pentenoic acid and 24.72g of DCC are dissolved in 250mLN, N' -dimethylformamide and stirred for reacting for 1h, then 25.76g of compound II-5 and 1.8g of DMAP are added, stirring is continued for 1.5h, then the temperature is raised to 40 ℃ and stirring is carried out for 12h, concentration and purification through column chromatography are carried out, thus obtaining purple solid I-12. The elemental analysis data are as follows: calculated values w (C) =64.75%, w (H) =4.25%, w (N) =9.44%; experimental values w (C) =65.08%, w (H) =4.22%, w (N) =9.39%.
Example 14 Synthesis of tetrakis [ (2-methyl-4-methylbutenyloxy) phenyl ] porphyrin (Compound I-13) the synthetic route for tetrakis [ (2-methyl-4-methylbutenyloxy) phenyl ] porphyrin (Compound I-13):
tetrakis [ (2-methyl-4-hydroxy) phenyl ] porphyrin (compound II-6) was prepared by the method of synthesis of compound II-1 according to example 1. Then at 0 ℃, dissolving 12.01g of methyl butenoic acid and 24.72g of DCC in 250mL of tetrahydrofuran, stirring for reaction for 1h, adding 22.05g of compound II-6 and 1.5g of DMAP, continuing stirring for 1.5h, raising the temperature to 40 ℃, stirring for 12h, concentrating, and performing column chromatography separation and purification to obtain a purple solid I-13. The elemental analysis data are as follows: calculated values w (C) =76.82%, w (H) =5.88%, w (N) =5.27%; experimental values w (C) =76.49%, w (H) =5.91%, w (N) =5.30%.
Example 15 Synthesis of Tetrakis [ (3-ethyl-4-methylpentanoyloxy) phenyl ] porphyrin (Compound I-14) Synthesis route to Tetrakis [ (3-ethyl-4-methylpentanoyloxy) phenyl ] porphyrin (Compound I-14):
tetrakis [ (3-ethyl-4-hydroxy) phenyl ] porphyrin (compound II-7) was prepared by the method of synthesis of compound II-1 according to example 1. And then dissolving 13.70g of methylpentenoic acid and 24.72g of DCC in 250mL of dichloromethane at the temperature of 0 ℃, stirring for reacting for 0.5h, adding 23.73g of compound II-7 and 1.5g of DMAP, continuing stirring for 1.5h, raising the temperature to 40 ℃, stirring for 12h, concentrating, and separating and purifying by column chromatography to obtain a purple solid I-14. The elemental analysis data are as follows: calculated w (C) =77.66%, w (H) =6.69%, w (N) =4.77%; experimental values w (C) =77.32%, w (H) =6.72%, w (N) =4.79%.
Example 16 Synthesis of tetrakis [ (3-trifluoromethyl-4-butenyloxy) phenyl ] porphyrin (Compound I-15) the synthetic route for tetrakis [ (3-trifluoromethyl-4-butenyloxy) phenyl ] porphyrin (Compound I-15):
tetrakis [ (3-trifluoromethyl-4-hydroxy) phenyl ] porphyrin (compound II-8) was prepared by referring to the synthesis method of compound II-1 of example 1. Then 10.32g of butenoic acid and 24.72g of DCC are dissolved in 250mLN and N' -dimethylformamide at the temperature of 0 ℃, stirred and reacted for 1h, then 28.52g of compound II-8 and 1.8g of DMAP are added, the stirring is continued for 1.5h, then the temperature is raised to 40 ℃, the stirring is carried out for 12h, the concentration is carried out, and the purple solid I-15 is obtained after the separation and purification by column chromatography. The elemental analysis data are as follows: calculated values w (C) =62.85%, w (H) =3.46%, w (N) =4.58%; experimental values w (C) =62.58%, w (H) =3.47%, w (N) =4.60%.
EXAMPLE 17 Synthesis of tetrakis [ (2, 4-dichloro-5-butenoyloxy) phenyl ] porphyrin (Compound I-16)
Synthetic route to tetrakis [ (2, 4-dichloro-5-butenyloxy) phenyl ] porphyrin (compound I-16):
tetrakis [ (2, 4-dichloro-5-hydroxy) phenyl ] porphyrin (compound II-9) was prepared by the method of synthesis of compound II-1 according to example 1. Then 10.32g of butenoic acid and 24.72g of DCC are dissolved in 250mLN and N' -dimethylformamide at the temperature of 0 ℃, stirred and reacted for 1h, then 28.63g of compound II-9 and 1.8g of DMAP are added, the stirring is continued for 1.5h, then the mixture is heated to 40 and stirred for 12h, concentrated and purified by column chromatography separation, and purple solid I-16 is obtained. The elemental analysis data are as follows: calculated values w (C) =58.75%, w (H) =3.12%, w (N) =4.57%; experimental values w (C) =59.02%, w (H) =3.13%, w (N) =4.55%.
EXAMPLE 18 Synthesis of tetrakis [ (3-isopropyl-5-methylbutenyloxy) phenyl ] porphyrin (Compound I-17)
The synthetic route of tetra [ (3-isopropyl-5-methylbutenyloxy) phenyl ] porphyrin (compound I-17):
tetrakis [ (3-isopropyl-5-hydroxy) phenyl ] porphyrin (compound II-10) was prepared by the method of synthesis of compound II-1 according to example 1. Then at 0 ℃, 12.01g of methyl butenoic acid and 24.72g of DCC are dissolved in 250mL of N, N' -dimethylformamide, stirred and reacted for 1h, then 25.41g of compound II-10 and 1.5g of DMAP are added, the mixture is continuously stirred for 1.5h, then the mixture is heated to 40 ℃ and stirred for 12h, concentrated and separated and purified by column chromatography, and the purple solid I-17 is obtained. The elemental analysis data are as follows: calculated w (C) =77.66%, w (H) =6.69%, w (N) =4.77%; experimental values w (C) =77.95%, w (H) =6.67%, w (N) =4.75%.
EXAMPLE 19 Synthesis of tetrakis [ (4-fluoro-3-pentenoyloxy) phenyl ] porphyrin (Compound I-18)
Synthetic route of tetrakis [ (4-fluoro-3-pentenoyloxy) phenyl ] porphyrin (compound I-18):
tetrakis [ (4-fluoro-3-hydroxy) phenyl ] porphyrin (compound II-11) was prepared by the method of synthesis of compound II-1 according to example 1. Then at 0 ℃, dissolving 12.01g of pentenoic acid and 24.72g of DCC in 250mL of chloroform, stirring for reacting for 1h, adding 22.52g of compound II-11 and 1.8g of DMAP, continuing stirring for 1.5h, raising the temperature to 40 ℃, stirring for 12h, concentrating, and separating and purifying by column chromatography to obtain a purple solid I-18. The elemental analysis data are as follows: calculated values w (C) =71.95%, w (H) =5.15%, w (N) =4.94%; experimental values w (C) =72.24%, w (H) =5.17%, w (N) =4.92%.
EXAMPLE 20 preparation of silica hydrogel Material selectively Filtering harmful blue light
The synthesis route of the silica hydrogel material for selectively filtering harmful blue light comprises the following steps:
16.38g of hydroxyethyl methacrylate (HEMA), 2.25g of methacryloxypropyl trimethoxy silicon hospital (KH-570), 3.38g of N-vinyl pyrrolidone (NVP), 0.05 percent of compound I-1 and 0.158g of initiator Azobisisobutyronitrile (AIBN) are mixed and stirred for 1 hour at room temperature, filtered, dripped into a mold, hermetically reacted for 8 hours in a drying oven at 90 ℃, demoulded and soaked in pure water for 10 hours to prepare the blue-light-proof silica hydrogel material.
EXAMPLE 21 preparation of silica hydrogel Material selectively Filtering harmful blue light
Mixing 16.38g HEMA, 2.25g KH-570, 3.38g NVP, 0.1% compound I-1 and 0.158g AIBN at room temperature, stirring for 1.5h, filtering, dripping into a mold, sealing in an oven at 90 ℃ for reaction for 8h, demolding, and soaking in pure water for 10h to obtain the blue-light-proof silica hydrogel material.
EXAMPLE 22 preparation of silica hydrogel Material selectively Filtering harmful blue light
The synthesis route of the silica hydrogel material for selectively filtering harmful blue light is as follows:
mixing 16.38g HEMA, 2.25g KH-570, 3.38g NVP, 0.05% compound I-2 and 0.158g AIBN at room temperature, stirring for 1h, filtering, dripping into a mold, sealing in an oven at 90 ℃ for reaction for 8h, demolding, and soaking in pure water for 10h to obtain the blue-light-proof silicon hydrogel material.
EXAMPLE 23 preparation of silica hydrogel Material selectively Filtering harmful blue light
Mixing 16.38g HEMA, 2.25g KH-570, 3.38g NVP, 0.1% compound I-2 and 0.158g AIBN at room temperature, stirring for 1.5h, filtering, dripping into a mold, sealing in an oven at 90 ℃ for reaction for 8h, demolding, and soaking in pure water for 10h to obtain the blue-light-proof silicon hydrogel material.
Comparative example 1 preparation of a silica hydrogel Material
Synthetic route for silicone hydrogel materials:
mixing 16.38g HEMA, 2.25g KH-570, 3.38g NVP, 0.158g AIBN and 0.338g N, N' -methylene bisacrylamide at room temperature, stirring for 1h, filtering, dripping into a mold, sealing and reacting in an oven at 90 ℃ for 8h, demolding, and soaking in pure water for 10h to obtain the silica hydrogel material.
EXAMPLE 24 preparation of hydrogel Material selectively Filtering unwanted blue light
Synthetic route of hydrogel material for selectively filtering harmful blue light:
mixing and stirring 20.01g of HEMA, 19.69g of NVP, 0.1g of Azobisisoheptonitrile (ABVN) and 0.05% of compound I-1 at room temperature for 2h, filtering, dripping into a mold, carrying out a closed reaction in an oven at 90 ℃ for 12h, demolding, and soaking in pure water for 10h to obtain the blue-light-proof hydrogel material.
EXAMPLE 25 preparation of hydrogel Material selectively Filtering unwanted blue light
Mixing and stirring 20.01g of HEMA, 19.69g of NVP, 0.1g of ABVN and 0.1% of compound I-1 at room temperature for 2h, filtering, dripping into a mold, sealing and reacting in an oven at 90 ℃ for 12h, demolding, and soaking in pure water for 10h to obtain the blue-light-proof hydrogel material.
Comparative example 2 preparation of hydrogel Material
Synthetic route for hydrogel materials:
mixing and stirring 20.01g of HEMA, 19.69g of NVP, 0.1g of ABVN and 0.2g of Ethylene Glycol Dimethacrylate (EGDMA) at room temperature for 2 hours, filtering, dripping into a mold, sealing and reacting in an oven at 90 ℃ for 12 hours, demolding, and soaking in pure water for 10 hours to prepare the hydrogel material.
EXAMPLE 26 preparation of hydrogel lenses selectively filtering harmful blue light
Mixing 39.56g of HEMA, 0.05 percent of compound I-1, 0.2g of AIBN and 0.2g of EGDMA at room temperature, stirring for 5 hours, filtering, dripping into a lens mould, reacting for 7 hours in an oven at 100 ℃, demoulding, putting into pure water for hydrating for 8 hours, and then transferring into standard saline to prepare the blue-light-proof hydrogel contact lens. (see FIG. 4)
Example 27 preparation of hydrogel lenses that selectively filter harmful blue light
Mixing 39.56g of HEMA, 0.1% of compound I-1, 0.2g of AIBN and 0.2g of EGDMA at room temperature, stirring for 5h, filtering, dripping into a lens mold, reacting in an oven at 100 ℃ for 7h, demolding, putting into pure water for hydrating for 8h, and transferring into standard saline to prepare the blue-light-proof hydrogel contact lens. (see FIG. 5)
Comparative example 3
Mixing 39.60g HEMA, 0.2g AIBN and 0.2g EGDMA at room temperature, stirring for 5h, filtering, dripping into a lens mold, reacting in an oven at 100 ℃ for 7h, demolding, putting into pure water for hydration for 8h, and transferring into standard saline to obtain the hydrogel contact lens. (see FIG. 6)
EXAMPLE 28 preparation of silica hydrogel lenses selectively rejecting harmful blue light
23.68g of 3-methacryloxypropyltris (trimethylsiloxy) silane (TRIS), 15.84g of N-methyl-N-Vinylacetamide (VMA), 0.05 percent of compound I-1, 0.2g of AIBN and 0.2g of EGDMA are mixed and stirred for 12 hours at room temperature, filtered, dripped into a lens mould, reacted for 12 hours in a 70 ℃ oven, demoulded, soaked in 20 percent ethanol solution for 1 hour, then transferred into pure water for hydration for 12 hours, and finally put into standard saline to prepare the blue-light-proof silicone hydrogel contact lens. (see FIG. 7)
Example 29 preparation of a silica hydrogel lens that selectively filters harmful blue light
23.68g of 3-methacryloxypropyltris (trimethylsiloxy) silane (TRIS), 15.84g of N-methyl-N-Vinylacetamide (VMA), 0.1 percent of compound I-1, 0.2g of AIBN and 0.2g of EGDMA are mixed and stirred for 12 hours at room temperature, filtered, dripped into a lens mould, reacted for 12 hours in a 70 ℃ oven, demoulded, soaked in 20 percent ethanol solution for 1 hour, then transferred into pure water for hydration for 12 hours, and finally put into standard saline to prepare the blue-light-proof silicone hydrogel contact lens. (see FIG. 8)
Comparative example 4
Mixing and stirring 23.68g of TRIS, 15.84g of VMA, 0.2g of AIBN and 0.2g of EGDMA at room temperature for 12h, filtering, dripping into a lens mold, reacting in an oven at 70 ℃ for 12h, demolding, soaking in 20% ethanol solution for 1h, then transferring into pure water for 12h of hydration, and finally putting into standard saline to prepare the silicon hydrogel contact lens. (see FIG. 9)
Performance test examples:
example 30 thermal stability
3mg of tetraarylporphyrin compounds containing alkenoic acid esters were weighed and subjected to Differential Scanning Calorimetry (DSC) to determine their decomposition temperatures. The compound was further baked at 100 deg.C, 150 deg.C and 200 deg.C for 1 hour, respectively, and the infrared absorption spectrum was measured by potassium bromide tabletting method. Some of the test results are shown in table 1 and fig. 10 to 12.
TABLE 1 DSC test results
Example 31 harmful blue light absorption Properties
Preparing 5 mu mol/L tetraaryl porphyrin compound solution containing olefine acid ester, and measuring the transmittance of the tetraaryl porphyrin compound solution at the wavelength of 220-800 nm by using ethyl acetate as a solvent; the high molecular material and the contact lens are tightly attached to the light transmission surface of the optical glass of the cuvette filled with standard saline (the formula of the standard saline is referred to GB 11417.4-2012), and the transmittance of the optical glass is measured at the wavelength of 220-800 nm. Some of the test results are shown in table 2.
TABLE 2 results of transmittance test
Claims (6)
1. A tetraaryl porphyrin compound containing olefine acid ester is characterized in that the structure is shown as a general formula I:
wherein: x1, X2, X3 and X4 are respectively and independently selected from one of hydrogen, halogen, cyano-group, nitro-group, alkyl, halogenated alkyl and alkyl carbonyl; the halogen is fluorine, chlorine, bromine or iodine; the halogenation in the halogenated alkyl is fluoro, chloro, bromo or iodo; r is selected from H or alkyl; n =1 or 2 or 3 or 4.
2. The tetraarylporphyrins containing alkenoic acid esters according to claim 1 wherein R is H or methyl or ethyl.
3. The tetraaryl porphyrins containing olefinic acid ester according to claim 1, wherein X1, X2, X3, and X4 are one of hydrogen, methyl, ethyl, fluorine, chlorine, trifluoromethyl, isopropyl, and nitro.
4. The tetraaryl porphyrin based compound with the alkenoic acid ester according to claim 1, wherein the structural formula of the compound is:
5. the use of tetraaryl porphyrins containing alkenoic acid esters as claimed in any one of claims 1 to 4 in the preparation of a polymer material for filtering high energy short wave blue light of 400 to 420 nm.
6. Use of tetraarylporphyrins containing alkenoic acid esters according to any one of claims 1 to 4 for the preparation of contact lenses.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115710277A (en) * | 2022-11-03 | 2023-02-24 | 江苏海伦隐形眼镜有限公司 | Ethylene glycol unit-containing alkenyl-terminated tetraaryl porphyrin compound and preparation method and application thereof |
| CN116715800A (en) * | 2023-05-15 | 2023-09-08 | 江苏海伦隐形眼镜有限公司 | Blue light resistant contact lens and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011237730A (en) * | 2010-05-13 | 2011-11-24 | Yamamoto Chem Inc | Spectacle lens |
| CN102279528A (en) * | 2010-06-10 | 2011-12-14 | 第一毛织株式会社 | Blue color resin composition for color filter and color filter using the same |
| US20140093661A1 (en) * | 2012-10-02 | 2014-04-03 | High Performance Optics, Inc. | Selective Blue Light Filtered Optic |
| CN105622620A (en) * | 2014-10-31 | 2016-06-01 | 北京大学 | Preparation method for porphyrin photosensitizer with visual photodynamic therapy characteristic |
| CN106543323A (en) * | 2015-09-23 | 2017-03-29 | 合肥炜烨光学科技有限公司 | A kind of cluster carrotene acrylate blue-light absorbers and preparation method thereof |
| CN106715442A (en) * | 2014-05-05 | 2017-05-24 | 尖端科学公司 | Photo-stable and thermally-stable dye compounds for selective blue light filtered optic |
| US20170235034A1 (en) * | 2014-05-05 | 2017-08-17 | Frontier Scientific, Inc. | Photo-stable and thermally-stable dye compounds for selective blue light filtered optic |
| JP2020015786A (en) * | 2018-07-23 | 2020-01-30 | 三井化学株式会社 | Lens, composition and method for manufacturing lens |
| CN111656229A (en) * | 2018-10-31 | 2020-09-11 | 株式会社Lg化学 | Blue light cut-off film, filter including the same, and display device |
| CN115215963A (en) * | 2021-04-19 | 2022-10-21 | 江苏海伦隐形眼镜有限公司 | Anti-blue-light corneal contact lens and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201418821A (en) * | 2012-10-02 | 2014-05-16 | High Performance Optics Inc | Selective blue light filtered optic |
-
2021
- 2021-04-19 CN CN202110422675.5A patent/CN115215874B/en active Active
- 2021-05-07 WO PCT/CN2021/092097 patent/WO2022222195A1/en active Application Filing
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011237730A (en) * | 2010-05-13 | 2011-11-24 | Yamamoto Chem Inc | Spectacle lens |
| CN102279528A (en) * | 2010-06-10 | 2011-12-14 | 第一毛织株式会社 | Blue color resin composition for color filter and color filter using the same |
| KR20110135185A (en) * | 2010-06-10 | 2011-12-16 | 제일모직주식회사 | Blue color resin composition for color filter and color filter using same |
| US20140093661A1 (en) * | 2012-10-02 | 2014-04-03 | High Performance Optics, Inc. | Selective Blue Light Filtered Optic |
| CN106715442A (en) * | 2014-05-05 | 2017-05-24 | 尖端科学公司 | Photo-stable and thermally-stable dye compounds for selective blue light filtered optic |
| US20170235034A1 (en) * | 2014-05-05 | 2017-08-17 | Frontier Scientific, Inc. | Photo-stable and thermally-stable dye compounds for selective blue light filtered optic |
| CN105622620A (en) * | 2014-10-31 | 2016-06-01 | 北京大学 | Preparation method for porphyrin photosensitizer with visual photodynamic therapy characteristic |
| CN106543323A (en) * | 2015-09-23 | 2017-03-29 | 合肥炜烨光学科技有限公司 | A kind of cluster carrotene acrylate blue-light absorbers and preparation method thereof |
| JP2020015786A (en) * | 2018-07-23 | 2020-01-30 | 三井化学株式会社 | Lens, composition and method for manufacturing lens |
| CN111656229A (en) * | 2018-10-31 | 2020-09-11 | 株式会社Lg化学 | Blue light cut-off film, filter including the same, and display device |
| CN115215963A (en) * | 2021-04-19 | 2022-10-21 | 江苏海伦隐形眼镜有限公司 | Anti-blue-light corneal contact lens and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "In Situ Catalytic Reaction for Solving the Aggregation of Hydrophobic Photosensitizers in Tumor" * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115710277A (en) * | 2022-11-03 | 2023-02-24 | 江苏海伦隐形眼镜有限公司 | Ethylene glycol unit-containing alkenyl-terminated tetraaryl porphyrin compound and preparation method and application thereof |
| CN115991710A (en) * | 2022-11-03 | 2023-04-21 | 江苏海伦隐形眼镜有限公司 | Blue light resistant cornea contact lens based on tetraarylporphyrin compound and preparation method thereof |
| CN115991709A (en) * | 2022-11-03 | 2023-04-21 | 江苏海伦隐形眼镜有限公司 | Alkenyl-terminated tetraaryl metalloporphyrin compound containing ethylene glycol unit, and preparation method and application thereof |
| CN115991847A (en) * | 2022-11-03 | 2023-04-21 | 江苏海伦隐形眼镜有限公司 | Blue light resistant cornea contact lens based on tetraaryl metalloporphyrin compound and preparation method thereof |
| CN115710277B (en) * | 2022-11-03 | 2023-12-08 | 江苏海伦隐形眼镜有限公司 | Alkenyl-terminated tetraarylporphyrin compound containing ethylene glycol unit, and preparation method and application thereof |
| CN115991847B (en) * | 2022-11-03 | 2023-12-08 | 江苏海伦隐形眼镜有限公司 | Blue light resistant cornea contact lens based on tetraaryl metalloporphyrin compound and preparation method thereof |
| CN115991710B (en) * | 2022-11-03 | 2023-12-08 | 江苏海伦隐形眼镜有限公司 | Blue light resistant cornea contact lens based on tetraarylporphyrin compound and preparation method thereof |
| CN115991709B (en) * | 2022-11-03 | 2023-12-08 | 江苏海伦隐形眼镜有限公司 | Alkenyl-terminated tetraaryl metalloporphyrin compound containing ethylene glycol unit, and preparation method and application thereof |
| WO2024093233A1 (en) * | 2022-11-03 | 2024-05-10 | 江苏海伦隐形眼镜有限公司 | Alkenyl-terminated tetraarylmetalloporphyrin compounds comprising ethylene glycol unit, preparation method therefor, and use thereof |
| CN116715800A (en) * | 2023-05-15 | 2023-09-08 | 江苏海伦隐形眼镜有限公司 | Blue light resistant contact lens and preparation method thereof |
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