Azacoumarin and azathiocoumarin derivatives for use in optically active devices

Abstract

The present invention relates to a new ophthalmic device comprising a polymeric compound containing a photoactive chromophore, to said polymeric compound, and to a specific monomeric compound particularly suitable for use in compositions and ophthalmic devices. The present invention also relates to a method of altering the optical properties of said ophthalmic device or of a precursor article used in the manufacture of said ophthalmic device.

Description

Technical Field

[0001] This invention relates to novel ophthalmic devices comprising polymeric compounds containing photoactive chromophores, said polymeric compounds, and specific monomeric compounds particularly suitable for compositions and ophthalmic devices. The invention also relates to a method for modifying the optical properties of said ophthalmic device or a precursor article used to manufacture said ophthalmic device. Background Technology

[0002] Cataracts are a general term for eye diseases that cause vision loss and, in extreme cases, blindness due to clouding of the eye's normally clear lens. It is a leading cause of blindness worldwide, affecting over 100 million people. Because its primary cause is age, and the average age of the population is constantly increasing, the number of cataract cases is expected to continue to rise significantly in the future.

[0003] Effective treatment for cataracts can only be achieved through surgical intervention, in which the eye's natural lens is removed through an incision in the cornea and replaced with an ophthalmic device (often called an "intraocular lens"). In preparation for surgery, current surgical methods employ ocular mapping to approximate the refractive power best suited to the individual patient.

[0004] Although cataract surgery is one of the most widely used and safest surgical procedures, it is not without specific postoperative problems. The refractive power of the implanted intraocular lens (IOL) is often insufficient to restore good vision. Such problems can arise, for example, from changes in the eye's geometry caused by the surgery, as well as irregular wound healing and positioning errors, which result in the ophthalmic device not having optimal optical properties. Therefore, patients will still need assistive devices for vision correction, such as glasses, to see properly. In some cases, the refractive power produced by the implanted ophthalmic device is far less than the required refractive power, necessitating further surgery. This is particularly undesirable for older adults, as the body's healing ability decreases with age. Furthermore, there is a risk of developing endophthalmitis, an inflammation of the eye that can even lead to complete vision loss, or worse, loss of the eye itself.

[0005] Therefore, the health sector needs optically active ophthalmic devices, specifically artificial intraocular lenses, which will allow for non-invasive adjustment of refractive power after lens implantation, thereby preferably further reducing the need for postoperative visual aids.

[0006] Some developments have been made in this sense, as demonstrated by, for example, WO 2007 / 033831, WO 2009 / 074520, US2010 / 0324165, WO 2017 / 032442, WO 2017 / 032443, WO 2017 / 032444, WO 2018 / 149850, WO2018 / 149852, WO 2018 / 149853, WO 2018 / 149855, WO 2018 / 149856, or WO 2018 / 149857.

[0007] M. Schraub et al., in European Polymer Journal 51 (2014) 21-27, described the photochemistry of polymethacrylates containing 3-phenyl-coumarin.

[0008] The synthesis of azacoumarins is known from literature such as RBMoffett, J. Org. Chem. 1970, 35(11), 3596-3600; D. Bonnetaud et al., J. Heterocycl. Chem. 1972, 9(1), 165-166D; F. Trécourt et al., J. Chem. Soc. Perkin Trans I, 1990, 2409-2415; Billeret et al., J. Heterocycl. Chem. 1993, 30(3), 671-674; G. Brufola et al., Heterocycles, 1997, 45, 9, 1715-1721; and D. Wang et al., Org. Lett. 2017, 19, 984-987, as well as from patent literature such as CN106810559.

[0009] The synthesis of pyranopyridones is known, for example, from O.S. Wolfbeis, Monatshefte für Chemie, 1982, 113, 365-370.

[0010] US4103256 describes a dye laser containing a laser dye solution of an azocoumarin compound.

[0011] JP8301849, JP8337583 and US5,585,385 describe heterocyclic compounds with tachykinin receptor antagonistic activity.

[0012] JP2004203751 describes a 6,6-heterocyclic derivative as an adrenocorticotropic hormone-releasing factor (corticotropic hormone) CRF (CRH) antagonist, which can be used for Alzheimer's disease and obesity.

[0013] CN106810560 describes a method for synthesizing azacoumarin derivatives and their application in antitumor drugs.

[0014] CN106810559 describes a selective inhibitor of a fibroblast growth factor receptor comprising a nitrogen-containing heterocyclic six-membered ring, wherein a double-bonded group is linked to a bicyclic ring via an N-phenyl-N group.

[0015] WO2007136125 and WO2007132948 describe compositions for inhibiting extracellular matrix gene transcription.

[0016] WO2007082178 describes prostaglandin reductase inhibitors.

[0017] WO2008094476 describes substituted pyrano[2,3-B]pyridine derivatives as cannabinoid-1 receptor modulators.

[0018] WO2010049269, WO2010049270, and WO2011117195 describe substituted pyridines and their use as herbicides. WO2011057942 describes substituted pyridines for insecticidal uses and for use in agricultural and veterinary fields. WO2012150550 describes aminopyranones as insecticidal compounds.

[0019] WO2018171688 describes compounds for the treatment and / or prevention of obesity and obesity-related conditions.

[0020] WO2000008026 describes the synthesis of a fused bicyclic heterocyclic fungicide.

[0021] US20070053831 describes a method for labeling structures such as β-amyloid plaques and neurofibrillary tangles in vivo or in vitro, the method comprising contacting brain tissue with specific azacoumarin compounds.

[0022] WO2009032754 describes compounds and methods that can be used as CB2 modulators to treat or prevent disease states.

[0023] US20110021522 describes azacoumarin compounds and related derivatives and pharmaceutical compositions as activators of procystein 3, 6 and / or 7.

[0024] WO2013130689 describes compounds for the treatment of spinal muscular atrophy.

[0025] WO2016146583 describes the synthesis of KV1.3 inhibitors and related starting materials.

[0026] However, there is still a need to provide alternative or improved ophthalmic devices, such as contact lenses or lenses implanted using existing cataract surgery methods, and there is still a need to provide special compounds for manufacturing ophthalmic devices, such as intraocular lenses implanted using existing cataract surgery methods, specifically using existing micro-incision cataract surgery methods.

[0027] Therefore, the purpose of this application is to provide alternative or improved ophthalmic devices and suitable compounds for manufacturing such ophthalmic devices.

[0028] Another object of this application is to provide compounds whose optical properties can be altered, preferably by non-invasive techniques.

[0029] Another object of this application is to provide alternative compounds or compounds having advantages over currently known compounds, preferably in combination with ophthalmic devices.

[0030] The advantage of monomers of formula (I) used to prepare ophthalmic devices according to the invention is that they are better handled by means of low melting points through their use in compositions and / or polymers / copolymers. Another advantage is that liquid to low melting point monomers of formula (I) used to prepare ophthalmic devices according to the invention allow for greater flexibility in the selection of initiators for thermally activated polymerization.

[0031] The advantages of polymers or copolymers comprising the polymeric monomers of formula (I) according to the invention are good flexibility and low glass transition temperature. The polymers or copolymers according to the invention preferably exhibit a significant change in polarization or refractive index after irradiation, as well as a partially increased initial refractive index. The total value of the refractive index change per mmol of photoactive chromophore is much higher compared to prior art materials. This allows for greater flexibility in adjusting the polarization or refractive index of ophthalmic devices according to the invention. Based on this advantage of the polymers or copolymers of the invention, ophthalmic devices comprising said materials can be manufactured thinner than ophthalmic devices comprising prior art materials. Summary of the Invention

[0032] The inventors have now discovered that the above-mentioned objectives can be achieved by ophthalmic devices and the compounds of this application, either alone or in any combination.

[0033] This invention relates to ophthalmic devices or precursor articles for manufacturing ophthalmic devices, comprising at least one polymeric compound of formula (I).

[0034]

[0035] in

[0036] Divalent group Groups selected from formulas (B-1), (B-2), (B-3), (B-4), or (B-5)

[0037]

[0038]

[0039] The asterisk * indicates a connection to the rest of equation (I);

[0040] Y1, Y2, Y3, and Y4 are each independently either CR' or N, provided that only one of Y1, Y2, Y3, and Y4 is N and the others are CR'.

[0041] Y5 is O, S, or NR. B ;

[0042] R B Each time it appears, it is independently selected from straight-chain or branched alkyl groups having 1 to 10 carbon atoms or from straight-chain or branched partially or fully fluorinated alkyl groups having 1 to 10 carbon atoms;

[0043] X is either O or S;

[0044] Y0 is either O or S;

[0045] A1, A2, A3, and A4 are each independently N, CR”, or CY-R2-R1, provided that if m1 is 1, then only one of A1, A2, A3, and A4 is N and the others are CR”, and provided that if m1 is 0, then only one of A1, A2, A3, and A4 is N, only one of A1, A2, A3, and A4 is CY-R2-R1 and the others are each independently CR”.

[0046] or

[0047] If m1 is 0, then the adjacent A1-A2, A2-A3 or A3-A4 are each independently -N(R2-R1)-C(=O)- or -C(=O)-N(R2-R1)-, and the remaining A3, A4, A1 and A2 are each independently CR”;

[0048] Y can be O, S, SO2 or bond independently;

[0049] m1 is 0 or 1;

[0050] n1 is 4;

[0051] n2 is 2;

[0052] R' is independently selected from the group consisting of the following each time it appears: H, F, SF5, CN, SO2CF3, straight-chain or branched, non-halogenated, partially or fully halogenated alkyl groups having 1 to 20 carbon atoms, non-halogenated, partially or fully halogenated cycloalkyl groups having 3 to 6 carbon atoms, straight-chain or branched, non-halogenated, partially or fully halogenated alkoxy groups having 1 to 20 carbon atoms, and straight-chain or branched, non-halogenated, partially or fully halogenated thioalkyl groups having 1 to 20 carbon atoms;

[0053] "R" is independently selected from the group consisting of the following each time it appears: H, F, Cl, Br, CN, SO2CF3, straight-chain or branched, non-halogenated, partially or fully halogenated alkyl groups having 1 to 20 carbon atoms, non-halogenated, partially or fully halogenated cycloalkyl groups having 3 to 6 carbon atoms, straight-chain or branched, non-halogenated, partially or fully halogenated alkoxy groups having 1 to 20 carbon atoms, and straight-chain or branched, non-halogenated and partially or fully halogenated thioalkyl groups having 1 to 20 carbon atoms.

[0054] R1 is a trialkoxysilyl group or a dialkoxyalkylsilyl group, wherein the alkyl and / or alkoxy groups are each independently a straight-chain or branched group having 1 to 6 carbon atoms, or a silyl group of formula (1), (2) or (3), or a polymerizable group of formula (4).

[0055]

[0056] Each alkyl group, when appearing independently, represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and each asterisk "*" independently represents a linking group -R2-, -R2-Y, or [Y-R2-]. m1 The connection;

[0057] And among them

[0058] X 11 Choose the groups composed of O, S, O-SO2, SO2-O, C(=O), OC(=O), C(=O)O, S(C=O), and (C=O)S.

[0059] R5, R6, and R7 are each independently selected from the group consisting of H, F, a straight-chain or branched, non-fluorinated, partially or fully fluorinated alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 14 carbon atoms, and each when they appear.

[0060] c is 0 or 1;

[0061] -R2- is –(C(R)2) o –or–(C(R)2)p –X8–(C(R)2) q –(X9) s –(C(R)2) r –(X 10 ) t -(C(R)2) u -;

[0062] R is independently selected each time it appears from the group consisting of H, F, straight-chain or branched alkyl groups having 1 to 4 carbon atoms, or straight-chain or branched partially or fully fluorinated alkyl groups having 1 to 4 carbon atoms;

[0063] Choose any group from 0 to 20.

[0064] X8, X9, X 10 Each occurrence is independently O, S, SO2, or NR0.

[0065] s and t are 0 or 1.

[0066] p and q are independently selected from groups of 1 to 10 each time they appear.

[0067] r and u are independently selected from groups of 0 to 10 each time they appear, where –(C(R)2) p –X8–(C(R)2) q –(X9) s –(C(R)2) r –(X 10 ) t -(C(R)2) u The total number of atoms in - is at most 20.

[0068] R0 is independently selected each time it appears from the group consisting of straight-chain or branched alkyl groups having 1 to 4 carbon atoms and straight-chain or branched partially or fully fluorinated alkyl groups having 1 to 4 carbon atoms;

[0069] R3 is H, F, Cl, Br, CN, or a straight-chain or branched, non-halogenated, partially or fully halogenated alkyl group having 1 to 20 C atoms;

[0070] If m1 is 0, then R4 is R', and

[0071] If m1 is 1, then R4 is R1.

[0072] The present invention also relates to a method for forming an ophthalmic device as described above or preferably as follows, or a precursor article for manufacturing an ophthalmic device, the method comprising the steps of:

[0073] - Provide a composition comprising at least one compound of formula (I) as described above or preferably as described below and / or an oligomer or polymer derived from the compound of formula (I) as described below or preferably as described below but leaving at least one reactive group for polymerization, and additional monomers and / or crosslinking agents and / or UV absorbers and / or free radical initiators optionally different from the compound of formula (I);

[0074] - Subsequently, an ophthalmic device or precursor article of the composition is formed.

[0075] The present invention also relates to a method for altering the optical properties of an ophthalmic device or a precursor article for manufacturing an ophthalmic device as described above or preferably as follows, the method comprising the steps of:

[0076] - Provide an ophthalmic device or precursor article using the method described above or preferably as follows, and

[0077] -The ophthalmic device or precursor article is then exposed to irradiation with a wavelength of at least 200 nm and at most 1500 nm.

[0078] The present invention also relates to ophthalmic devices or precursor articles for manufacturing ophthalmic devices, which can be obtained by the method of modifying the optical properties as described above or preferably as described below.

[0079] The present invention also relates to oligomers, polymers or copolymers comprising at least one polymeric compound of formula (I) as described above or preferably as follows.

[0080] The present invention also relates to compositions for polymerization comprising at least one compound of formula (I) as described above or preferably as described below and / or an oligomer or polymer derived from a compound of formula (I) as described above or preferably as described below leaving at least one reactive group for polymerization and / or a crosslinking agent and / or a UV absorber and / or a free radical initiator and alternatively a monomer different from the compound of formula (I).

[0081] This invention also relates to compounds of formula (I),

[0082]

[0083] in

[0084] Divalent group Groups selected from formulas (B-1), (B-2), (B-3), (B-4), or (B-5)

[0085]

[0086] The asterisk * indicates a connection to the rest of equation (I);

[0087] Y1, Y2, Y3, and Y4 are each independently either CR' or N, provided that only one of Y1, Y2, Y3, and Y4 is N and the others are CR'.

[0088] Y5 is O, S, or NR. B ;

[0089] R B Each time it appears, it is independently selected from straight-chain or branched alkyl groups having 1 to 10 carbon atoms or from straight-chain or branched partially or fully fluorinated alkyl groups having 1 to 10 carbon atoms;

[0090] A1, A2, A3, and A4 are each independently N, CR”, or CY-R2-R1, provided that if m1 is 1, then only one of A1, A2, and A3 is N and the others and A4 are CR”, and provided that if m1 is 0, then only one of A1, A2, and A3 is N, only one of A1, A2, A3, and A4 is CY-R2-R1 and the others are each independently CR”.

[0091] or

[0092] If m1 is 0, then the adjacent A1-A2, A2-A3 or A3-A4 are each independently -N(R2-R1)-C(=O)- or -C(=O)-N(R2-R1)-, and the remaining A3, A4, A1 and A2 are each independently CR”;

[0093] Y can be O, S, SO2 or bond independently;

[0094] m1 is 0 or 1;

[0095] n1 is 4;

[0096] n2 is 2;

[0097] R' is independently selected from the group consisting of the following each time it appears: H, F, SF5, CN, SO2CF3, straight-chain or branched, non-halogenated, partially or fully halogenated alkyl groups having 1 to 20 carbon atoms, non-halogenated, partially or fully halogenated cycloalkyl groups having 3 to 6 carbon atoms, straight-chain or branched, non-halogenated, partially or fully halogenated alkoxy groups having 1 to 20 carbon atoms, and straight-chain or branched, non-halogenated, partially or fully halogenated thioalkyl groups having 1 to 20 carbon atoms;

[0098] "R" is independently selected from the group consisting of the following each time it appears: H, F, Cl, Br, CN, SO2CF3, straight-chain or branched, non-halogenated, partially or fully halogenated alkyl groups having 1 to 20 carbon atoms, non-halogenated, partially or fully halogenated cycloalkyl groups having 3 to 6 carbon atoms, straight-chain or branched, non-halogenated, partially or fully halogenated alkoxy groups having 1 to 20 carbon atoms, and straight-chain or branched, non-halogenated and partially or fully halogenated thioalkyl groups having 1 to 20 carbon atoms.

[0099] R1 is a trialkoxysilyl group or a dialkoxyalkylsilyl group, wherein the alkyl and / or alkoxy groups are each independently a straight-chain or branched group having 1 to 6 carbon atoms, or a silyl group of formula (1), (2) or (3), or a polymerizable group of formula (4).

[0100]

[0101] Each alkyl group, when appearing independently, represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and each asterisk "*" independently represents a linking group -R2-, -R2-Y, or [Y-R2-]. m1 The connection;

[0102] And among them

[0103] X 11 Choose the groups composed of O, S, O-SO2, SO2-O, C(=O), OC(=O), C(=O)O, S(C=O), and (C=O)S.

[0104] R5, R6, and R7 are each independently selected from the group consisting of H, F, a straight-chain or branched, non-fluorinated, partially or fully fluorinated alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 14 carbon atoms, and each when they appear.

[0105] c is 0 or 1;

[0106] -R2- is –(C(R)2) o –or–(C(R)2) p –X8–(C(R)2) q –(X9) s –(C(R)2) r –(X 10 ) t -(C(R)2) u -;

[0107] R is independently selected each time it appears from the group consisting of H, F, straight-chain or branched alkyl groups having 1 to 4 carbon atoms, or straight-chain or branched partially or fully fluorinated alkyl groups having 1 to 4 carbon atoms;

[0108] o is between 0 and 20.

[0109] X8, X9, X 10 Each occurrence is independently O, S, SO2, or NR0.

[0110] s and t are 0 or 1.

[0111] p and q are independently selected from groups of 1 to 10 each time they appear.

[0112] r and u are independently selected from groups of 0 to 10 each time they appear, where –(C(R)2) p –X8–(C(R)2) q –(X9) s –(C(R)2) r –(X 10 ) t -(C(R)2) u The total number of atoms in - is at most 20.

[0113] R0 is independently selected each time it appears from the group consisting of straight-chain or branched alkyl groups having 1 to 4 carbon atoms and straight-chain or branched partially or fully fluorinated alkyl groups having 1 to 4 carbon atoms;

[0114] R3 is H, F, Cl, Br, CN, or a straight-chain or branched, non-halogenated, partially or fully halogenated alkyl group having 1 to 20 C atoms;

[0115] If m1 is 0, then R4 is R', and

[0116] If m1 is 1, then R4 is R1;

[0117] The prerequisite is that if m1 is 0, then Y is 0 or S, and A2 is CY-R2-R1.

[0118] Divalent group It is in the 3rd position and is selected from equations (B-3) and (B-4), where Y4 in equation (B-3) is N, and Y3 in equation (B-4) is N, and c is 1;

[0119] The prerequisite is that if m1 is 1, then A2 is CR” and R” is a straight-chain or branched, non-halogenated, partially or fully halogenated alkoxy group having 1 to 20 carbon atoms and a straight-chain or branched, non-halogenated and partially or fully halogenated thioalkyl group having 1 to 20 carbon atoms.

[0120] Divalent group It is in the 3rd position and is selected from formula (B-3), where Y2 in formula (B-3) is CR' and R' is H, Y4 in formula (B-3) is N, and Y is a bond, O or S, and c is 1;

[0121] The prerequisite is that if m1 is 1, then Y is a bond, c is 0, R3 is Cl, and...

[0122] Divalent group It is in the 3rd position, with o ranging from 5 to 20;

[0123] The prerequisite is that if m1 is 0, then Y is a bond or O, c is 0, R3 is Cl, and...

[0124] Divalent group It is in the 3rd position, with o ranging from 7 to 20;

[0125] The prerequisite is that if m1 is 0, then X is 0, Y0 is 0 and Y is a bond, c is 1, and X... 11 It is O, S, O-SO2, SO2-O, OC(=O), C(=O)O, S(C=O) and (C=O)S;

[0126] The prerequisite is that if m1 is 1, then X is 0 and Y0 is 0, and o is 5 to 20;

[0127] The prerequisite is that if m1 is 1, then c is 0, Y is a bond or 0, and...

[0128] Divalent group It is in the 3rd position, with o ranging from 11 to 20;

[0129] The prerequisite is that if m1 is 1, then A1 or A3 is N, Y is a bond, and c is 0.

[0130] Divalent group It is in the 3rd position, with o ranging from 7 to 20, and

[0131] The prerequisites are: if m1 is 0, then X is 0, Y0 is 0, Y is 0 or S, c is 0, A2 is CY-R2-R1, A3 is Br, and A1 is N.

[0132] Divalent group It is in the 4th position and is selected from formulas (B-1), (B-3) and (B-4), where o is 2 to 20. Detailed Implementation

[0133] Compounds of formula (I) as described above or preferably as follows can preferably be used as monomers for preparing precursor articles such as preforms, which can be converted into ophthalmic devices such as eye implants or specifically intraocular lenses, or can preferably be used to prepare ophthalmic devices as described above or preferably as follows.

[0134] All preferred embodiments of compounds of formula (I) and compounds of formula (I) containing any monomeric unit according to the invention include all stereoisomers or racemic mixtures.

[0135] Compared to prior art materials used in the preparation of ophthalmic devices as described above or in the manufacture of precursor articles for ophthalmic devices, compounds of formula (I) offer several advantages. Furthermore, compared to the aforementioned prior art compounds, the addition of a nitrogen atom to the left-hand aromatic portion of the central chromophore in compounds of formula (I) or oligomers, polymers, and copolymers containing polymers of formula (I) has a significant impact on optical properties.

[0136] Polymers that are foldable at room temperature typically exhibit a glass transition temperature (T0) below room temperature (approximately 21°C). g They are easily deformed at this temperature without causing physical damage to the polymer, such as by inducing creep, stress, or cracking. For polymers in intraocular lenses, a temperature below or equal to 15°C is suitable. g It is the preferred option.

[0137] Polymers used in the manufacture of ophthalmic devices, preferably intraocular lenses, preferably have a relatively high refractive index, which enables the manufacture of thinner ophthalmic devices such as intraocular lenses. Preferably, the polymer used in ophthalmic devices, preferably intraocular lenses, will have a refractive index greater than about 1.5, and currently most preferably greater than about 1.55.

[0138] If an asterisk ("*") is used in the specification of this invention, it indicates a connection to an adjacent unit or group, or, in the case of a polymer, a connection to an adjacent repeating unit or any other group, unless otherwise specifically defined.

[0139] A straight-chain or branched alkyl group having 1 to 10 carbon atoms means an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, such as methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl or 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl or 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-heptyl, n-octyl, ethylhexyl, n-nonyl or n-decyl. Straight-chain or branched alkyl groups having 1 to 20 carbon atoms include all examples of straight-chain or branched alkyl groups having 1 to 10 carbon atoms, including any alkyl group having 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 carbon atoms, such as n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecanyl, and n-eicosyl.

[0140] The term "partially halogenated alkyl group" means that at least one H atom of the alkyl group is replaced by F, Cl, Br, or I. Preferably, the alkyl group is partially fluorinated, meaning that at least one H atom of the alkyl group is replaced by F. A preferred partially halogenated alkyl group is CH2CF3.

[0141] The term "fully halogenated alkyl group" means that all the hydrogen atoms in the alkyl group are replaced by F, Cl, Br, and / or I. Preferably, the alkyl group is fully fluorinated, meaning that all the hydrogen atoms in the alkyl group are replaced by F. Preferred fully fluorinated alkyl groups are trifluoromethyl or pentafluoroethyl.

[0142] The term halogenation or preferably fluorination also corresponds to other groups, such as halogenated cycloalkyl groups, halogenated alkoxy groups, or halogenated thioalkyl groups.

[0143] Cycloalkyl groups having 3 to 6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, which can be partially or completely halogenated or fluorinated as described above. Preferably, the cycloalkyl group is cyclopropyl.

[0144] A straight-chain or branched alkoxy group having 1 to 20 carbon atoms represents an O-alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms, such as methoxy, ethoxy, isopropoxy, n-propoxy, isobutoxy, n-butoxy, tert-butoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, or 3-methylbutoxy, 1,1-dimethylpropoxy The alkoxy group, 1,2-dimethylpropoxy or 2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, ethylhexyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecanyloxy, n-hexadecyloxy, n-heptadecyloxy, n-octadecyloxy, n-nonadecanyloxy, and n-eicosyloxy, may be partially or completely halogenated or preferably partially or completely fluorinated. The preferred fully fluorinated alkoxy group is trifluoromethoxy.

[0145] A straight-chain or branched thioalkyl group having 1 to 20 carbon atoms represents an S-alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms, such as thiomethyl, 1-thioethyl, 1-thioisopropyl, 1-thion-propyl, 1-thioisobutyl, 1-thion-butyl, 1-thiotert-butyl, 1-thion-pentyl, 1-thio-1-methylbutyl, 1-thio-2-methylbutyl, or 1-thio-3-methylbutyl, 1-thio-1,1-dimethylpropyl, 1-thio-1,2-dimethylbutyl... -Dimethylpropyl or 1-thio-2,2-dimethylpropyl, 1-thio-1-ethylpropyl, 1-thiohexyl, 1-thioheptyl, 1-thiooctyl, 1-thioethylhexyl, 1-thiononyl, 1-thiodecyl, 1-thioundecyl, 1-thiododecyl, 1-thiotridecyl, 1-thiotetradecyl, 1-thiopentadecanyl, 1-thiohexadecyl, 1-thioheptadecyl, 1-thioheptadecyl, 1-thiooctadecyl, 1-thiononadecanyl, and 1-thioeicosyl, which may be partially or completely halogenated or preferably partially or completely fluorinated. The preferred fully fluorinated sulfide group is trifluoromethyl sulfide.

[0146] Preferred alkyl and alkoxy groups have 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 C atoms.

[0147] In the context of this invention, an aryl group contains 6 to 40 ring atoms, and in the context of this invention, a heteroaryl group contains 5 to 40 ring atoms comprising at least one heteroatom. The heteroatom is preferably selected from N, O, and / or S. The aryl group or heteroaryl group is to be understood herein to mean a simple aromatic ring, i.e., a phenyl group, or a simple heteroaromatic ring, such as pyridyl, pyrimidinyl, thiopheneyl, etc., or a fused (cyclofused) aryl or heteroaryl group, such as naphthyl, anthraceneyl, phenanthryl, quinolinyl, or isoquinolinyl.

[0148] The aryl group or heteroaryl group is preferably derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, benzo[a]anthracene, chrysoprase, perylene, fluoranthene, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, biphenylene oxide, terphenyl, triphenylene, fluorene, spirodifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans indo[a]fluorene, cis or trans indo[a]carbazole, cis or trans indo[a]carbazole, trimer indene, isotrimer indene, spirotrimer indene, spiroisotrimer indene, furan, benzo[a]furan, isobenzo[a]furan, dibenzo[a]furan, thiophene, benzene Thiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenothiazine, pyrazole, indazole, imidazole, benzimidazole, naphthimazole, phenanthrimazole, pyridylimazole, pyrazinylimazole, quinoxalineimazole, oxazole, benzoxazole, naphthimazole, anthrazole, phenanthrazole, isoxazole, 1,2-thiazole, 1,3-thiazole Azole, benzothiazole, pyridazine, hexaazatribenzene, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazathane, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluorouracil, naphthidine, azacarbazole, benzocarbline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole Azole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetraazine, 1,2,3,4-tetraazine, 1,2,3,5-tetraazine, purine, pteridine, indazine, and benzothiadiazole.

[0149] Polymerizable groups are groups that can undergo or be polymerized to form oligomers or polymers.

[0150] Polymerization is the process of taking individual monomers and linking them together to prepare longer units. These longer units are called polymers. Compounds of formula (I) as described above and preferably as follows are suitable monomers for preparing ophthalmic devices or for manufacturing precursor articles of ophthalmic devices.

[0151] Within the scope of this invention, once the polymerizable group R1 oligomerizes or polymerizes, it thereby forms or becomes part of the backbone of an oligomer, polymer, or copolymer comprising a polymeric compound of formula (I). A suitable polymerizable group is defined as...

[0152] Trialkoxysilyl group or dialkoxyalkylsilyl group, wherein the alkyl and / or alkoxy groups are each independently a straight-chain or branched group having 1 to 6 carbon atoms, or a silyl group of formula (1), (2) or (3), or a polymerizable group of formula (4).

[0153]

[0154] Each alkyl group, when appearing independently, represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and each asterisk "*" independently represents a linking group -R2-, -R2-Y, or [Y-R2-]. m1 The connection;

[0155] And among them

[0156] X 11 Choose the groups composed of O, S, O-SO2, SO2-O, C(=O), OC(=O), C(=O)O, S(C=O), and (C=O)S.

[0157] R5, R6, and R7 are each independently selected from the group consisting of H, F, a straight-chain or branched, non-fluorinated, partially or fully fluorinated alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 14 carbon atoms, and each when they appear.

[0158] c is 0 or 1.

[0159] The particularly preferred polymerizable groups are described below. The particularly preferred polymerizable groups are described below.

[0160] The aryl group having 6 to 14 carbon atoms is preferably an aryl group selected from the group consisting of phenyl, naphthyl or anthracene, and particularly preferably phenyl.

[0161] In a preferred embodiment, the compound of formula (I) that serves as a precursor article for the preparation of the ophthalmic device as described above, or for the manufacture of an ophthalmic device, or as a monomer for the preparation of an oligomer, polymer, or copolymer according to the invention, or that serves as a compound according to the invention, contains a polymerizable group R1 linked to a photoactive ring system via -R2- and Y. This is also true for compounds of formula (I) in which m1 is 0, which can be correspondingly described in formula (I').

[0162] Therefore, the present invention also relates to ophthalmic devices or precursor articles for manufacturing ophthalmic devices, comprising at least one polymeric compound of formula (I').

[0163]

[0164] Among them, R1, -R2-, Y, R3, X, Y0, R', R” and

[0165]

[0166] It has the meaning as described above, or preferably as described above, or as follows, and

[0167] A1, A2, A3, and A4 are each independently N, CR”, or CY-R2-R1, provided that only one of A1, A2, A3, and A4 is N, only one of A1, A2, A3, and A4 is CY-R2-R1, and the others are each independently CR”.

[0168] or

[0169] Each of the adjacent A1-A2, A2-A3 or A3-A4 is independently -N(R2-R1)-C(=O)- or -C(=O)-N(R2-R1)-, and the remaining A3, A4, A1 and A2 are independently CR” and R4 is R'.

[0170] Therefore, the present invention also relates to compounds of formula (I), wherein m1 is 0, which can preferably be described according to formula (I').

[0171]

[0172] Among them, R1, -R2-, Y, R3, X, Y0, R', R” and

[0173]

[0174] It has the meaning as described above, or preferably as described above, or as follows, and

[0175] A1, A2, A3, and A4 are each independently N, CR”, or CY-R2-R1, provided that only one of A1, A2, and A3 is N, only one of A1, A2, A3, and A4 is CY-R2-R1, and the others are each independently CR”.

[0176] or

[0177] Adjacent A1-A2, A2-A3, or A3-A4 are each independently -N(R2-R1)-C(=O)- or -C(=O)-N(R2-R1)-, and the remaining A3, A4, A1, and A2 are each independently CR” and R4 is R'.

[0178] The prerequisite is that if Y is O or S, A2 is CY-R2-R1, and

[0179] Divalent group It is in the 3rd position and is selected from equations (B-3) and (B-4), where Y4 in equation (B-3) is N, and Y3 in equation (B-4) is N, and c is 1;

[0180] The prerequisite is that if Y is a bond or O, then c is 0, R3 is Cl, and

[0181] Divalent group It is in the 3rd position, with o ranging from 7 to 20;

[0182] The prerequisite is that if X is 0, then Y0 is 0 and Y is a bond, c is 1, and X... 11 The terms are O, S, O-SO2, SO2-O, OC(=O), C(=O)O, S(C=O) and (C=O)S, and

[0183] The prerequisites are: if X is 0, then Y0 is 0, Y is 0 or S, c is 0, A2 is CY-R2-R1, A3 is Br, and A1 is N.

[0184] Divalent group It is in the 4th position and is selected from formulas (B-1), (B-3) and (B-4), where o is 2 to 20.

[0185] The positions of the substituents R1-R2-Y or R1-R2- in formula (I) or (I') are determined by the positions of A1, A2, A3, A4, A1-A2, A2-A3, and A3-A4.

[0186] In compounds of formula (I'-a), substituent A1 is CY-R2-R1 at position 8 of the photoactive chromophore, and A2, A3, and A4 have the meanings described above for compounds of formula (I) or (I'). In compounds of formula (I'-a), A2 is preferably N.

[0187] In compounds of formula (I'-b), substituent A2 is CY-R2-R1 at position 7 of the photoactive chromophore, and A1, A3, and A4 have the meanings described above for compounds of formula (I) or (I'). In compounds of formula (I'-b), A1 or A3 is preferably N.

[0188] In compounds of formula (I'-c), substituent A3 is CY-R2-R1 at position 6 of the photoactive chromophore, and A1, A2, and A4 have the meanings described above for compounds of formula (I) or (I'). In compounds of formula (I'-c), A1 or A2 is preferably N.

[0189] In compounds of formula (I'-d), substituent A4 is CY-R2-R1 at position 5 of the photoactive chromophore, and A1, A2, and A3 have the meanings described above for compounds of formula (I) or (I'). In compounds of formula (I'-d), A1 or A2 is preferably N.

[0190] In compounds of formula (I'-e), the substituents A1-A2 are -N(R2-R1)-CO-, and A3 and A4 have the meanings described above for compounds of formula (I) or (I').

[0191] In compounds of formula (I'-f), the substituents A1-A2 are -CO-N(R2-R1)-, and A3 and A4 have the meanings described above for compounds of formula (I) or (I').

[0192] In compounds of formula (I'-g), the substituents A2-A3 are -N(R2-R1)-CO-, and A1 and A4 have the meanings described above for compounds of formula (I) or (I').

[0193] In compounds of formula (I'-h), the substituents A2-A3 are -CO-N(R2-R1)-, and A1 and A4 have the meanings described above for compounds of formula (I) or (I').

[0194] In compounds of formula (I'-i), the substituents A3-A4 are -N(R2-R1)-CO-, and A1 and A2 have the meanings described above for compounds of formula (I) or (I').

[0195] Therefore, the present invention also relates to ophthalmic devices or precursor articles for manufacturing ophthalmic devices, comprising at least one polymeric compound of formula (I), wherein m1 is 0, which may preferably be described according to formulas (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), and (I'-i).

[0196]

[0197]

[0198] Among them, R1, -R2-, X, Y0, Y, A1, A2, A3, A4, R3, R4 and

[0199] It has the meaning as described above, or preferably as described above, or as follows.

[0200] Therefore, the present invention also relates to compounds of formula (I), wherein n is 1 and m1 is 0, which can preferably be described according to formulas (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h) and (I'-i) as described above, wherein R1, -R2-, X, Y0, Y, A1, A2, A3, A4, R3, R4 and

[0201] It has the meaning as described above or preferably as described above or as follows, and the disclaimers given therein must be used as disclosed in this invention.

[0202] The preferred position of R1-R2-YC or R1-R2-N is, for example, the 8th and / or 7th position of the photoactive chromophore visible in formulas (I'-a), (I'-b), (I'-e), (I'-g), and (I'-f).

[0203] In another preferred embodiment of the invention, the compound of formula (I) that serves as a precursor article for the preparation of the ophthalmic device as described above, or for the manufacture of an ophthalmic device, or as a monomer for the preparation of an oligomer, polymer, or copolymer according to the invention, or as a compound according to the invention as described above, contains a polymerizable group R1 connected to a divalent group linked to a photoactive chromophore via -R2- and Y-. This is true for compounds of formula (I) in which m1 is 1, which can be correspondingly described in formula (I”).

[0204] Therefore, the present invention also relates to ophthalmic devices or precursor articles for manufacturing ophthalmic devices, comprising at least one polymeric compound of formula (I”).

[0205]

[0206] Among them, R1, -R2-, Y, R3, X, Y0, R', R” and

[0207]

[0208] It has the meaning as described above, or preferably as described above, or as follows, and

[0209] "A1, A2, A3, and A4 are each independently N or CR", provided that only one of A1, A2, A3, and A4 is N and the others are CR.

[0210] Therefore, the present invention also relates to compounds of formula (I), wherein m1 is 1, which can preferably be described according to formula (I”).

[0211]

[0212] Among them, R1, -R2-, Y, R3, X, Y0, R', R” and

[0213]

[0214] It has the meaning as described above, or preferably as described above, or as follows, and

[0215] A1, A2, A3, and A4 are each independently N or CR, provided that only one of A1, A2, and A3 is N and the others and A4 are CR.

[0216] The prerequisite is that A2 is CR” and R” is a straight-chain or branched, non-halogenated, partially or fully halogenated alkoxy group having 1 to 20 carbon atoms and a straight-chain or branched, non-halogenated and partially or fully halogenated thioalkyl group having 1 to 20 carbon atoms.

[0217] Divalent group It is in the 3rd position and is selected from formula (B-3), where Y2 in formula (B-3) is CR' and R' is H, Y4 in formula (B-3) is N, and Y is a bond, O or S, and c is 1;

[0218] The prerequisite is that if Y is a bond, then c is 0, R3 is Cl, and...

[0219] Divalent group It is in the 3rd position, with o ranging from 5 to 20;

[0220] The prerequisite is that if X is 0 and Y0 is 0, then o is between 5 and 20;

[0221] The prerequisite is that if c is 0, then Y is either a bond or an 0, and

[0222] Divalent group In the 3rd position, o ranges from 11 to 20, and

[0223] The prerequisite is that if A1 or A3 is N, then Y is a bond and c is 0.

[0224] Divalent group It is in the 3rd position, with o ranging from 7 to 20;

[0225] As described above, in ophthalmic devices, precursor articles for manufacturing ophthalmic devices, compounds according to formulas (I), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) or (I”) according to the invention, and any oligomers, polymers or copolymers derived therefrom, the substituent R” is independently selected from the group consisting of: H, F, Cl, Br, CN, SO2CF3, straight-chain or branched, non-halogenated, partially or fully halogenated alkyl groups having 1 to 20 C atoms, non-halogenated, partially or fully halogenated cycloalkyl groups having 3 to 6 C atoms, straight-chain or branched, non-halogenated, partially or fully halogenated alkoxy groups having 1 to 20 C atoms, and straight-chain or branched, non-halogenated and partially or fully halogenated thioalkyl groups having 1 to 20 C atoms.

[0226] R” is preferably, in each occurrence, independently H, F, Cl, Br, CN, or a straight-chain or branched, non-halogenated, partially or fully halogenated alkyl group having 1 to 20 C atoms. R” is particularly preferably H.

[0227] As described above, in ophthalmic devices, precursor articles for manufacturing ophthalmic devices, compounds according to formulas (I), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), and (I'-h), (I'-i), or (I'") according to the invention, and any oligomers, polymers, or copolymers derived therefrom, the divalent groups Groups selected from formulas (B-1), (B-2), (B-3), (B-4), or (B-5)

[0228]

[0229] An asterisk * indicates a connection to the rest of the expression (I), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), or (I”).

[0230] Y1, Y2, Y3, and Y4 are each independently either CR' or N, provided that only one of Y1, Y2, Y3, and Y4 is N and the others are CR'.

[0231] Y5 is O, S, or NR. B ;

[0232] R B Each time it appears, it is independently selected from straight-chain or branched alkyl groups having 1 to 10 carbon atoms, or from straight-chain or branched partially or fully fluorinated alkyl groups having 1 to 10 carbon atoms. R B Preferably, it is a straight-chain or branched alkyl group having 1 to 4 C atoms or a partially or fully fluorinated alkyl group having 1 to 4 C atoms.

[0233] In the group of formula (B-5), Y5 is preferably O or S.

[0234] In one embodiment of the present invention, the divalent group Preferably, it is a group of formula (B-1) to (B-4).

[0235] In one embodiment of the present invention, the divalent group Preferably, it is a group of formula (B-1).

[0236] As described above, in ophthalmic devices, precursor articles for manufacturing ophthalmic devices, compounds according to formulas (I), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) or (I”) according to the invention, and any oligomers, polymers or copolymers derived therefrom, or within groups (B-1) to (B-5), the substituent R' is independently selected each time it appears. The group consisting of the following: H, F, SF5, CN, SO2CF3, straight-chain or branched, non-halogenated, partially or fully halogenated alkyl groups having 1 to 20 carbon atoms, non-halogenated, partially or fully halogenated cycloalkyl groups having 3 to 6 carbon atoms, straight-chain or branched, non-halogenated, partially or fully halogenated alkoxy groups having 1 to 20 carbon atoms, and straight-chain or branched, non-halogenated, partially or fully halogenated thioalkyl groups having 1 to 20 carbon atoms.

[0237] R' is preferably, independently and each time it appears, H, F, SF5, CN, SO2CF3, a straight-chain or branched, non-halogenated, partially or fully halogenated alkyl group having 1 to 10 carbon atoms, a non-halogenated, partially or fully halogenated cycloalkyl group having 3 to 6 carbon atoms, a straight-chain or branched, non-halogenated, partially or fully halogenated alkoxy group having 1 to 10 carbon atoms, and a straight-chain or branched, non-halogenated, partially or fully halogenated thioalkyl group having 1 to 10 carbon atoms.

[0238] In one embodiment of the invention, preferably all R's are H.

[0239] In one embodiment of the invention, preferably one R' is different from H, and the other substituents R' are selected from the list described above.

[0240] In one embodiment of the invention, preferably the two R's are different from H, and the other substituents R' are selected from the list described above.

[0241] R' is independently and particularly preferably selected from the group consisting of F, CN, SO2CF3, SF5, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, methoxy, ethoxy, propoxy, trifluoromethoxy, pentafluoroethoxy, thiomethyl and thioethyl.

[0242] R' is independently and particularly preferably selected from the group consisting of F, ethyl, n-pentyl, trifluoromethyl, methoxy and trifluoromethoxy.

[0243] Regarding the compounds according to the invention, the disclaimer must take into account the definition of R'.

[0244] As described above, in ophthalmic devices, precursor articles for manufacturing ophthalmic devices, compounds according to formulas (I), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), or (I”) according to the invention, and any oligomers, polymers, or copolymers derived therefrom, R3 is H, F, Cl, Br, CN, or a straight-chain or branched, non-halogenated, partially or fully halogenated alkyl group having 1 to 20 carbon atoms. Preferably, R3 is H, F, or a straight-chain or branched, non-halogenated, partially or fully halogenated alkyl group having 1 to 10 carbon atoms. Particularly preferably, R3 is H.

[0245] As described above, in ophthalmic devices, precursor articles for manufacturing ophthalmic devices, compounds according to formulas (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), or (I'-i) according to the invention, and any oligomers, polymers, or copolymers derived therefrom, R4 is R', and R' has the meaning described above or preferably as described above.

[0246] As described above, in ophthalmic devices, precursor articles for manufacturing ophthalmic devices, compounds according to formulas (I), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) or (I”) according to the invention, and any oligomers, polymers or copolymers derived therefrom, X is O or S, preferably O.

[0247] As described above, in ophthalmic devices, precursor articles for manufacturing ophthalmic devices, compounds according to formulas (I), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) or (I”) according to the invention, and any oligomers, polymers or copolymers derived therefrom, Y0 is O or S, preferably O.

[0248] Furthermore, the present invention also relates to ophthalmic devices or precursor articles for manufacturing ophthalmic devices, comprising at least one polymeric compound of formula (I), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), or (I”) as described above or preferably as described above, wherein X is O and Y0 is O.

[0249] In these embodiments of the invention, when m1 is 0 and R4 is R', the substitution mode of group (B-1) is preferably selected from (S-1) to (S-12).

[0250]

[0251] Wherein R' independently has the meaning as described above or preferably as follows. Preferred substitution modes are (S-1), (S-7), (S-10), (S-11), and (S-12). Particularly preferred substitution modes are (S-7) and / or (S-10) and / or (S-12). Very particularly preferred substitution mode is (S-7). Very particularly preferred substitution mode is (S-10). Very particularly preferred substitution mode is (S-12).

[0252] As described above, in formula (I) or formula (I”), if m1 is 1, then the substituent R4 corresponds to R1, wherein R’ in the divalent groups of formulas (B-1) to (B-5) has the meaning described above or the preferred or particularly preferred meaning described above.

[0253] In this embodiment where R4 is R1 and R1 is connected to a divalent group of formulas (B-1) to (B-4) via -R2-Y-, such R1-R2-Y- groups are preferably located at the ortho, meta, or para position of the bond connecting the divalent group to the remainder of formula (I) or (I”). In this embodiment where R4 is R1 and R1 is connected to a divalent group via -R2-Y-, such R1-R2-Y- groups are particularly preferably located at the ortho or para position of the bond connecting the divalent group of formulas (B-1), (B-2), or (B-4) to the remainder of formula (I) or (I”). In this embodiment where R4 is R1 and R1 is connected to a divalent group via -R2-Y-, such R1-R2-Y- groups are very particularly preferably located at the para position of the bond connecting the divalent group of formulas (B-1) or (B-2) to the remainder of formula (I) or (I”).

[0254] Therefore, the present invention also relates to ophthalmic devices or precursor articles for manufacturing ophthalmic devices, comprising polymeric compounds of formula (I) or (I”), wherein R4 is R1, and R’ has the meaning as described above or preferably as follows, and R1 is attached to a divalent group via -R2-Y-, and such R1-R2-Y- groups are located in the ortho or para position of the bonds of the divalent groups of formulas (B-1), (B-2), and (B-4) attached to the remainder of formula (I) or (I”).

[0255] The divalent group as described above, or preferably as described above. The preferred position is the third position of the photoactive chromophore.

[0256] The following formula summarizes the R3 and divalent groups of compounds of formula (I) read as formula (I#). The preferred location

[0257]

[0258] Where R1, -R2-, X, Y0, Y, R3, R4, m1, A1, A2, A3, and A4 have the meanings described above or preferably as described above or as follows. Such compounds according to formula (I#) preferably serve as monomers of formula (I) for the preparation of ophthalmic devices as described above, or as precursor articles for the manufacture of ophthalmic devices, or for the preparation of oligomers, polymers, or copolymers according to the invention.

[0259] According to the present invention, compounds of formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), and (I”) having substituents as described above or preferably as described above have polymerizable groups as described above or preferably as described above or as follows and have at least one linking element Y-R2 or -R2-.

[0260] According to the present invention, Y is independently O, S, O=S=O or a bond each time it appears.

[0261] According to the present invention, the connecting element R2 is selected from –(C(R)2). o –or–(C(R)2) p –X8–(C(R)2) q –(X9) s –(C(R)2) r –(X 10 ) t -(C(R)2) u - The group consisting of R, which is independently selected each time it appears, from H, F, straight-chain or branched alkyl groups having 1 to 4 carbon atoms, or straight-chain or branched partially or fully fluorinated alkyl groups having 1 to 4 carbon atoms, and o is selected from the group consisting of 1 to 20, X8, X9 and X 10 Each occurrence is O, S, SO2 or NR0, s and t are independently 0 or 1 each time they occur, p and q are independently selected from the group of 1 to 10 each time they occur, r and u are independently selected from the group of 0 to 10 each time they occur, where –(C(R)2) p –X8–(C(R)2) q –(X9) s –(C(R)2) r –(X 10 ) t -(C(R)2) u The total number of atoms is at most 20 C atoms. R0 in NR0 is independently selected, each time from the group consisting of a straight-chain or branched alkyl group having 1 to 4 C atoms and a straight-chain or branched partially or fully fluorinated alkyl group having 1 to 4 C atoms. R0 is independently and preferably methyl, ethyl, or trifluoromethyl in each occurrence. R0 is particularly preferably methyl in each occurrence.

[0262] According to the present invention, R is independently selected from the group consisting of H, F, straight-chain or branched alkyl groups having 1 to 8 C atoms, or straight-chain or branched partially or fully fluorinated alkyl groups having 1 to 4 C atoms each time it appears.

[0263] R is particularly preferably independent of H, F, methyl, or ethyl in each occurrence. R is very particularly preferably H.

[0264] In another preferred embodiment of the invention, in compounds of formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), and (I”) that act as precursor articles for the preparation of ophthalmic devices as described above or for the manufacture of ophthalmic devices, or for the preparation of oligomers, polymers, or copolymers according to the invention, or in compounds according to the invention, o is preferably selected from the group consisting of 7, 8, 9, 10, 11, 12, 13, and 14. Preferably, o is selected from the group consisting of 5, 6, 7, 8, 9, 10, 11, 12, and 13. Particularly preferably, o is selected from the group consisting of 8, 9, 10, 11, and 12. Regarding compounds according to the invention, the disclaimer must take into account the definition of o.

[0265] In another preferred embodiment of the invention, in compounds of formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), and (I”) that act as precursor articles for the preparation of ophthalmic devices as described above or for the manufacture of ophthalmic devices, or for the preparation of oligomers, polymers, or copolymers according to the invention, or in compounds according to the invention, s, t, X8, X9, X 10 p, q, r, and u have the following preferred meanings:

[0266] Preferably, s is 1. Preferably, s is 0.

[0267] Preferably, t is 0 or 1.

[0268] Preferably, s and t are both 0.

[0269] Preferably, X8, X9 and X 10 It is O, S, or SO2. Particularly preferred are X8, X9, and X 10 For O. Particularly preferred are X8, X9, and X. 10 For S. Particularly preferred are X8, X9, and X. 10 It is SO2.

[0270] Preferably, p and q are each independently 1, 3, 3, 4, 5 or 6, particularly preferably 1 or 2, and very particularly preferably 2.

[0271] Preferably, r and u are each independently 0, 1, 2 or 3, particularly preferably 0, 1 or 2, and very particularly preferably 0.

[0272] If o is 0, then -R2- is the key.

[0273] According to the present invention, suitable examples of -R2- are -(CH2)-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)9-, and -(CH2) 10 -、-(CH2) 11 -、-(CH2) 12 -、-(CH2) 13 -、-(CH2) 14 -、-(CH2) 15 -、-(CH2) 16 -、-(CH2) 17 -、-(CH2) 18 -、-(CH2) 19 -、-(CH2) 20 -, -(CHCH3)-, -(CHCH3)2-, -(CHCH3)3-, -(CHCH3)4-, -(CHCH3)5-, -(CHCH3)6-, -(CHCH3)7-, -(CHCH3)8-, -(CHCH3)9-, -(CHCH3) 10 -、-(CHCH3) 11 -、-(CHCH3) 12 -、-(CHCH3) 13 -、-(CHCH3) 14 -、-(CHCH3) 15 -、-(CHCH3) 16 -、-(CHCH3) 17 -、-(CHCH3) 18 -、-(CHCH3) 19 -、-(CHCH3) 20 -, -(C(CH3)2)-, -(C(CH3)2)2-, -(C(CH3)2)3-, -(C(CH3)2)4-, -(C(CH3)2)5-, -(C(CH3)2)6-, -(C(CH3)2)7-, -(C(CH3)2)8-, -(C(CH3)2)9-, -(C(CH3)2) 10 -、-(C(CH3)2) 11 -、-(C(CH3)2) 12 -、-(C(CH3)2) 13-、-(C(CH3)2) 14 -、-(C(CH3)2) 15 -、-(C(CH3)2) 16 -、-(C(CH3)2) 17 -、-(C(CH3)2) 18 -、-(C(CH3)2) 19 -、-(C(CH3)2) 20 -、-(CHC2H5)-、-(CHC2H5)2-、-(CHC2H5)3-、-(CHC2H5)4-、-(CHC2H5)5-、-(CHC2H5)6-、-(CHC2H5)7-、-(CHC2H5)8-、-(CHC2H5)9-、-(CHC2H5) 10 -、-(CHC2H5) 11 -、-(CHC2H5) 12 -、-(CHC2H5) 13 -、-(CHC2H5) 14 -、-(CHC2H5) 15 -、-(CHC2H5) 16 -、-(CHC2H5) 17 -、-(CHC2H5) 18 -、-(CHC2H5) 19 -、-(CHC2H5) 20 -、-(CH2)-(CHCH3)-(CH2)-、-(CH2)-(CHCH3)-(CH2)2-、-(CH2)-(CHCH3)-(CH2)3-、-(CH2)-(CHCH3)-(CH2) 11 -、-(CH2)2-(CHCH3)-(CH2)-、-(CH2)3-(CHCH3)-(CH2)-、-(CH2) 11-(CHCH3)-(CH2)-、-(CH2)2-O-(CH2)2-、-(CH2)3-O-(CH2)3-、-(CH2)2-O -(CH2)2-O-(CH2)2-、-(CH2)3-O-(CH2)3-O-(CH2)3-、-(CH2)2-O-(CH2)2 -O-(CH2)6-、-(CH2)6-O-(CH2)2-O-(CH2)2-、-(CH2)2-O-(CH2)2-O-(CH2 )8-、-(CH2)8-O-(CH2)2-O-(CH2)2-、-(CH2)2-S-(CH2)2-、-(CH2)3-S-(C H2)3-、-(CH2)2-S-(CH2)2-S-(CH2)2-、-(CH2)3-S-(CH2)3-S-(CH2)3-、- (CH2)2-S-(CH2)2-S-(CH2)6-、-(CH2)6-S-(CH2)2-S-(CH2)2-、-(CH2)2- S-(CH2)2-S-(CH2)8-、-(CH2)8-S-(CH2)2-S-(CH2)2-、-(CH2)2-SO2-(CH2)2-、-(CH2)3-SO2-(CH2)3-、-(CH2)2-SO2-(CH2)2-SO2-(CH2)2-、-(CH2) 3-SO2-(CH2)3-SO2-(CH2)3-、-(CH2)2-SO2-(CH2)2-SO2-(CH2)6-、-(CH2)6-SO2-(CH2)2-SO2-(CH2)2-、-(CH2)2-SO2-(CH2)2-SO2-(CH2)8-、-(CH2)8-SO2-(CH2)2-SO2-(CH2)2-、-(CH2)-S-(CH2)2-O-(CH2)-、-(CH2)-SO2-(CH2)2-O-(CH2)-、-(CH2)-SO2-(CH2)2-S-(CH2)-、-(CH2)-O-(CH2)2-S -(CH2)2-O-(CH2)-、-(CH2)-S-(CH2)2-O-(CH2)2-S-(CH2)-、-(CH2)-SO2-(CH2)2-SO2-(CH2)-、-(CH2)-S-(CH2)2-S-(CH2)2-S-(CH2)-、-(CH2)-SO2-(CH2)2-SO2-(CH2)2-SO2-(CH2)-、-(CH2)-O-(CH2)2-SO2-(CH2)2-O-(CH2)-、-(CH2)2-(NCH3)-(CH2)2-、-(CH2)3-(NCH3)-(CH2)3-、-(CH2)2-(NCH3)-(CH2)2-(NCH3)-(CH2)2-, -(CH2)3-(NCH3)-(CH2)3-(NCH3)-(CH2)3-, -(CH2)2-(NCH3)-(CH2)2-(NCH3)-(CH2)6-, -(CH2)6-(NCH3)-(CH2)2-(NCH3)-(CH2)2-, -(CH2)2-(NCH3)-(CH2)2-(NCH3)-(CH2)8- and -(CH2)8-(NCH3)-(CH2)2-(NCH3)-(CH2)2-;

[0274] -(CF2)-(CH2)-, -(CH2)-(CF2)-, -(CH2)-(CF2)-(CH2)-, -(CH2)-(CF2)-(CH2)2-, -(CH2)-(CF2)-(CH2)3-, -(CH2)-(CF2)-(CH2)4-, -(CH2) -(CF2)-(CH2)5-, -(CH2)-(CF2)-(CH2)6-, -(CH2)-(CF2)-(CH2)7-, -(CH2)-(CF2)-(CH2)8-, -(CH2)-(CF2)-(CH2)9-, -(CH2)-(CF2)-(CH2) 10 -, -(CH2)2-(CF2)-(CH2)-, -(CH2)3-(CF2)-(CH2)-, -(CH2)4-(CF2)-(CH2)-, -(CH2)5-(CF2)-(CH2)-, -( CH2)6-(CF2)-(CH2)-, -(CH2)7-(CF2)-(CH2)-, -(CH2)8-(CF2)-(CH2)-, -(CH2)9-(CF2)-(CH2)-, -(CH2) 10-(CF2)-(CH2)-、-(CH2)2-(CF2)-(CH2)2-、-(CH2)3-(CF2)-(CH2)3-、-(CH2)4-(CF2)-(CH2)4-、-(CH2)5-(CF2)-(CH2)5-、-(CH2)2-(CF2)-(CH2)-、-(CH2)2-(CF2)-(CH2)3-、-(CH2)2-(CF2)-(CH2)4-、-(CH2)2-(CF2)-(CH2)5-、-(CH2)2-(CF2)-(CH2)6-、-(CH2)2-(CF2)-(CH2)7-、-(CH2)2-(CF2)-(CH2)8-、-(CH2)2-(CF2)-(CH2)9-、-(CH2)3-(CF2)-(CH2)-、-(CH2)3-(CF2)-(CH2)2-、-(CH2)3-(CF2)-(CH2)4-、-(CH2)3-(CF2)-(CH2)5-、-(CH2)3-(CF2)-(CH2)6-、-(CH2)3-(CF2)-(CH2)7-、-(CH2)3-(CF2)-(CH2)8-、-(CH2)4-(CF2)-(CH2)-、-(CH2)4-(CF2)-(CH2)2-、-(CH2)4-(CF2)-(CH2)3-、-(CH2)4-(CF2)-(CH2)5-、-(CH2)4-(CF2)-(CH2)6-、-(CH2)4-(CF2)-(CH2)7-、-(CH2)5-(CF2)-(CH2)-、-(CH2)5-(CF2)-(CH2)2-、-(CH2)5-(CF2)-(CH2)3-、-(CH2)5-(CF2)-(CH2)4-、-(CH2)5-(CF2)-(CH2)6-、-(CH2)6-(CF2)-(CH2)-、-(CH2)6-(CF2)-(CH2)2-、-(CH2)6-(CF2)-(CH2)3-、-(CH2)6-(CF2)-(CH2)4-、-(CH2)6-(CF2)-(CH2)5-、

[0275] -(CFH)-(CH2)-、-(CH2)-(CFH)-、-(CH2)-(CFH)-(CH2)-、-(CH2)-(CFH)-(CH2)2-、-(CH2)-(CFH)-(CH2)3-、-(CH2)-(CFH)-(CH2)4-、-(CH2)-(CFH)-(CH2)5-、-(CH2)-(CFH)-(CH2)6-、-(CH2)-(CFH)-(CH2)7-、-(CH2)-(CFH)-(CH2)8-、-(CH2)-(CFH)-(CH2)9-、-(CH2)-(CFH)-(CH2) 10 -、-(CH2)2-(CFH)-(CH2)-、-(CH2)3-(CFH)-(CH2)-、-(CH2)4-(CFH)-(CH2)-、-(CH2)5-(CFH)-(CH2)-、-(CH2)6-(CFH)-(CH2)-、-(CH2)7-(CFH)-(CH2)-、-(CH2)8-(CFH)-(CH2)-、-(CH2)9-(CFH)-(CH2)-、-(CH2) 10-(CFH)-(CH2)-、-(CH2)2-(CFH)-(CH2)2-、-(CH2)3-(CFH)-(CH2)3-、-(CH2)4-(CFH)-(CH2)4-、-(CH2)5-(CFH)-(CH2)5-、-(CH2)2-(CFH)-(CH2)-、-(CH2)2-(CFH)-(CH2)3-、-(CH2)2-(CFH)-(CH2)4-、-(CH2)2-(CFH)-(CH2)5-、-(CH2)2-(CFH)-(CH2)6-、-(CH2)2-(CFH)-(CH2)7-、-(CH2)2-(CFH)-(CH2)8-、-(CH2)2-(CFH)-(CH2)9-、-(CH2)3-(CFH)-(CH2)-、-(CH2)3-(CFH)-(CH2)2-、-(CH2)3-(CFH)-(CH2)4-、-(CH2)3-(CFH)-(CH2)5-、-(CH2)3-(CFH)-(CH2)6-、-(CH2)3-(CFH)-(CH2)7-、-(CH2)3-(CFH)-(CH2)8-、-(CH2)4-(CFH)-(CH2)-、-(CH2)4-(CFH)-(CH2)2-、-(CH2)4-(CFH)-(CH2)3-、-(CH2)4-(CFH)-(CH2)5-、-(CH2)4-(CFH)-(CH2)6-、-(CH2)4-(CFH)-(CH2)7-、-(CH2)5-(CFH)-(CH2)-、-(CH2)5-(CFH)-(CH2)2-、-(CH2)5-(CFH)-(CH2)3-、-(CH2)5-(CFH)-(CH2)4-、-(CH2)5-(CFH)-(CH2)6-、-(CH2)6-(CFH)-(CH2)-、-(CH2)6-(CFH)-(CH2)2-、-(CH2)6-(CFH)-(CH2)3-、-(CH2)6-(CFH)-(CH2)4-、-(CH2)6-(CFH)-(CH2)5-、

[0276] -(CF2)2-(CH2)-、-(CH2)-(CF2)2-、-(CH2)-(CF2)2-(CH2)-、-(CH2)-(CF2)2-(CH2)2-、-(CH2)-(CF2)2-(CH2)3-、-(CH2)-(CF2)2-(CH2)4-、-(CH2)-(CF2)2-(CH2)5-、-(CH2)-(CF2)2-(CH2)6-、-(CH2)-(CF2)2-(CH2)7-、-(CH2)-(CF2)2-(CH2)8-、-(CH2)-(CF2)2-(CH2)9-、-(CH2)2-(CF2)2-(CH2)-、-(CH2)3-(CF2)2-(CH2)-、-(CH2)4-(CF2)2-(CH2)-、-(CH2)5-(CF2)2-(CH2)-、-(CH2)6-(CF2)2-(CH2)-、-(CH2)7-(CF2)2-(CH2)-、-(CH2)8-(CF2)2-(CH2)-、-(CH2)9-(CF2)2-(CH2)-、-(CH2)2-(CF2)2-(CH2)2-、-(CH2)3-(CF2)2-(CH2)3-、-(CH2)4-(CF2)2-(CH2)4-、-(CH2)5-(CF2)2-(CH2)5-、-(CH2)2-(CF2)2-(CH2)-、-(CH2)2-(CF2)2-(CH2)3-、-(CH2)2-(CF2)2-(CH2)4-、-(CH2)2-(CF2)2-(CH2)5-、-(CH2)2-(CF2)2-(CH2)6-、-(CH2)2-(CF2)2-(CH2)7-、-(CH2)2-(CF2)2-(CH2)8-、-(CH2)3-(CF2)2-(CH2)-、-(CH2)3-(CF2)2-(CH2)2-、-(CH2)3-(CF2)2-(CH2)4-、-(CH2)3-(CF2)2-(CH2)5-、-(CH2)3-(CF2)2-(CH2)6-、-(CH2)3-(CF2)2-(CH2)7-、-(CH2)4-(CF2)2-(CH2)-、-(CH2)4-(CF2)2-(CH2)2-、-(CH2)4-(CF2)2-(CH2)3-、-(CH2)4-(CF2)2-(CH2)5-、-(CH2)4-(CF2)2-(CH2)6-、-(CH2)5-(CF2)2-(CH2)-、-(CH2)5-(CF2)2-(CH2)2-、-(CH2)5-(CF2)2-(CH2)3-、-(CH2)5-(CF2)2-(CH2)4-、-(CH2)6-(CF2)2-(CH2)-、-(CH2)6-(CF2)2-(CH2)2-、-(CH2)6-(CF2)2-(CH2)3-、-(CH2)6-(CF2)2-(CH2)4-、

[0277] -(CFH)2-(CH2)-、-(CH2)-(CFH)2-、-(CH2)-(CFH)2-(CH2)-、-(CH2)-(CFH)2-(CH2)2-、-(CH2)-(CFH)2-(CH2)3-、-(CH2)-(CFH)2-(CH2)4-、-(CH2)-(CFH)2-(CH2)5-、-(CH2)-(CFH)2-(CH2)6-、-(CH2)-(CFH)2-(CH2)7-、-(CH2)-(CFH)2-(CH2)8-、-(CH2)-(CFH)2-(CH2)9-、-(CH2)2-(CFH)2-(CH2)-、-(CH2)3-(CFH)2-(CH2)-、-(CH2)4-(CFH)2-(CH2)-、-(CH2)5-(CFH)2-(CH2)-、-(CH2)6-(CFH)2-(CH2)-、-(CH2)7-(CFH)2-(CH2)-、-(CH2)8-(CFH)2-(CH2)-、-(CH2)9-(CFH)2-(CH2)-、-(CH2)2-(CFH)2-(CH2)2-、-(CH2)3-(CFH)2-(CH2)3-、-(CH2)4-(CFH)2-(CH2)4-、-(CH2)5-(CFH)2-(CH2)5-、-(CH2)2-(CFH)2-(CH2)-、-(CH2)2-(CFH)2-(CH2)3-、-(CH2)2-(CFH)2-(CH2)4-、-(CH2)2-(CFH)2-(CH2)5-、-(CH2)2-(CFH)2-(CH2)6-、-(CH2)2-(CFH)2-(CH2)7-、-(CH2)2-(CFH)2-(CH2)8-、-(CH2)3-(CFH)2-(CH2)-、-(CH2)3-(CFH)2-(CH2)2-、-(CH2)3-(CFH)2-(CH2)4-、-(CH2)3-(CFH)2-(CH2)5-、-(CH2)3-(CFH)2-(CH2)6-、-(CH2)3-(CFH)2-(CH2)7-、-(CH2)4-(CFH)2-(CH2)-、-(CH2)4-(CFH)2-(CH2)2-、-(CH2)4-(CFH)2-(CH2)3-、-(CH2)4-(CFH)2-(CH2)5-、-(CH2)4-(CFH)2-(CH2)6-、-(CH2)5-(CFH)2-(CH2)-、-(CH2)5-(CFH)2-(CH2)2-、-(CH2)5-(CFH)2-(CH2)3-、-(CH2)5-(CFH)2-(CH2)4-、-(CH2)6-(CFH)2-(CH2)-、-(CH2)6-(CFH)2-(CH2)2-、-(CH2)6-(CFH)2-(CH2)3-、-(CH2)6-(CFH)2-(CH2)4-、

[0278] -(CF2)3-(CH2)-、-(CH2)-(CF2)3-、-(CH2)-(CF2)3-(CH2)-、-(CH2)-(CF2)3-(CH2)2-、-(CH2)-(CF2)3-(CH2)3-、-(CH2)-(CF2)3-(CH2)4-、-(CH2)-(CF2)3-(CH2)5-、-(CH2)-(CF2)3-(CH2)6-、-(CH2)-(CF2)3-(CH2)7-、-(CH2)-(CF2)3-(CH2)8-、-(CH2)2-(CF2)3-(CH2)-、-(CH2)3-(CF2)3-(CH2)-、-(CH2)4-(CF2)3-(CH2)-、-(CH2)5-(CF2)3-(CH2)-、-(CH2)6-(CF2)3-(CH2)-、-(CH2)7-(CF2)3-(CH2)-、-(CH2)8-(CF2)3-(CH2)-、-(CH2)2-(CF2)3-(CH2)2-、-(CH2)3-(CF2)3-(CH2)3-、-(CH2)4-(CF2)3-(CH2)4-、-(CH2)2-(CF2)3-(CH2)-、-(CH2)2-(CF2)3-(CH2)3-、-(CH2)2-(CF2)3-(CH2)4-、-(CH2)2-(CF2)3-(CH2)5-、-(CH2)2-(CF2)3-(CH2)6-、-(CH2)2-(CF2)3-(CH2)7-、-(CH2)3-(CF2)3-(CH2)-、-(CH2)3-(CF2)3-(CH2)2-、-(CH2)3-(CF2)3-(CH2)4-、-(CH2)3-(CF2)3-(CH2)5-、-(CH2)3-(CF2)3-(CH2)6-、-(CH2)4-(CF2)3-(CH2)-、-(CH2)4-(CF2)3-(CH2)2-、-(CH2)4-(CF2)3-(CH2)3-、-(CH2)4-(CF2)3-(CH2)5-、-(CH2)5-(CF2)3-(CH2)-、-(CH2)5-(CF2)3-(CH2)2-、-(CH2)5-(CF2)3-(CH2)3-、-(CH2)5-(CF2)3-(CH2)4-、(CH2)6-(CF2)3-(CH2)-、-(CH2)6-(CF2)3-(CH2)2-、-(CH2)6-(CF2)3-(CH2)3-、

[0279] -(CF2)4-(CH2)-、-(CH2)-(CF2)4-、-(CH2)-(CF2)4-(CH2)-、-(CH2)-(CF2)4-(CH2)2-、-(CH2)-(CF2)4-(CH2)3-、-(CH2)-(CF2)4-(CH2)4-、-(CH2)-(CF2)4-(CH2)5-、-(CH2)-(CF2)4-(CH2)6-、-(CH2)-(CF2)4-(CH2)7-、-(CH2)-(CF2)4-(CH2)8-、-(CH2)-(CF2)4-(CH2)9-、-(CH2)-(CF2)4-(CH2) 10 -、-(CH2)2-(CF2)4-(CH2)-、-(CH2)3-(CF2)4-(CH2)-、-(CH2)4-(CF2)4-(CH2)-、-(CH2)5-(CF2)4-(CH2)-、-(CH2)6-(CF2)4-(CH2)-、-(CH2)7-(CF2)4-(CH2)-、-(CH2)2-(CF2)4-(CH2)2-、-(CH2)3-(CF2)4-(CH2)3-、-(CH2)4-(CF2)4-(CH2)4-、-(CH2)5-(CF2)4-(CH2)5-、-(CH2)2-(CF2)4-(CH2)3-、-(CH2)2-(CF2)4-(CH2)4-、-(CH2)2-(CF2)4-(CH2)5-、-(CH2)2-(CF2)4-(CH2)6-、-(CH2)3-(CF2)4-(CH2)2-、-(CH2)3-(CF2)4-(CH2)4-、-(CH2)4-(CF2)4-(CH2)2-、-(CH2)4-(CF2)4-(CH2)3-、-(CH2)5-(CF2)4-(CH2)2-、-(CH2)5-(CF2)4-(CH2)3-、-(CH2)6-(CF2)4-(CH2)2-、

[0280] -(CF2)5-(CH2)-、-(CH2)-(CF2)5-、-(CH2)-(CF2)5-(CH2)-、-(CH2)-(CF2)5-(CH2)2-、-(CH2)-(CF2)5-(CH2)3-、-(CH2)-(CF2)5-(CH2)4-、-(CH2)-(CF2)5-(CH2)5-、-(CH2)-(CF2)5-(CH2)6-、-(CH2)2-(CF2)5-(CH2)-、-(CH2)3-(CF2)5-(CH2)-、-(CH2)4-(CF2)5-(CH2)-、-(CH2)5-(CF2)5-(CH2)-、-(CH2)6-(CF2)5-(CH2)-、-(CH2)2-(CF2)5-(CH2)2-、-(CH2)3-(CF2)5-(CH2)3-、-(CH2)4-(CF2)5-(CH2)4-、-(CH2)2-(CF2)5-(CH2)3-、-(CH2)2-(CF2)5-(CH2)4-、-(CH2)2-(CF2)5-(CH2)5-、-(CH2)2-(CF2)5-(CH2)6-、-(CH2)3-(CF2)5-(CH2)2-、-(CH2)3-(CF2)5-(CH2)4-、-(CH2)4-(CF2)5-(CH2)2-、-(CH2)4-(CF2)5-(CH2)3-、-(CH2)5-(CF2)5-(CH2)2-、

[0281] -(CHCF3)-(CH2)-、-(CH2)-(CHCF3)-、-(CH2)-(CHCF3)-(CH2)-、-(CH2)-(CHCF3)-(CH2)2-、-(CH2)-(CHCF3)-(CH2)3-、-(CH2)-(CHCF3)-(CH2)4-、-(CH2)-(CHCF3)-(CH2)5-、-(CH2)-(CHCF3)-(CH2)6-、-(CH2)-(CHCF3)-(CH2)7-、-(CH2)-(CHCF3)-(CH2)8-、-(CH2)-(CHCF3)-(CH2)9-、-(CH2)-(CHCF3)-(CH2) 10-、-(CH2)2-(CHCF3)-(CH2)-、-(CH2)3-(CHCF3)-(CH2)-、-(CH2)4-(CHCF3)-(CH2)-、-(CH2)5-(CHCF3)-(CH2)-、-(CH2)6-(CHCF3)-(CH2)-、-(CH2)7-(CHCF3)-(CH2)-、-(CH2)8-(CHCF3)-(CH2)-、-(CH2)9-(CHCF3)-(CH2)-、-(CH2) 10 -(CHCF3)-(CH2)-、-(CH2)2-(CHCF3)-(CH2)2-、-(CH2)3-(CHCF3)-(CH2)3-、-(CH2)4-(CHCF3)-(CH2)4-、-(CH2)5-(CHCF3)-(CH2)5-、-(CH2)2-(CHCF3)-(CH2)3-、-(CH2)2-(CHCF3)-(CH2)4-、-(CH2)2-(CHCF3)-(CH2)5-、 -(CH2)2-(CHCF3)-(CH2)6-、-(CH2)2-(CHCF3)-(CH2)7-、-(CH2)2-(CHCF3)-(CH2)8-、-(CH2)2-(CHCF3)-(CH2)9-、-(CH2)3-(CHCF3)-(CH2)2-、-(CH2)3-(CHCF3)-(CH2)4-、-(CH2)3-(CHCF3)-(CH2)5-、-(CH2)3-(CHCF3)- (CH2)6-、-(CH2)3-(CHCF3)-(CH2)7-、-(CH2)3-(CHCF3)-(CH2)8-、-(CH2)4-(CHCF3)-(CH2)2-、-(CH2)4-(CHC) F3)-(CH2)3-、-(CH2)4-(CHCF3)-(CH2)5-、-(CH2)4-(CHCF3)-(CH2)6-、-(CH2)4-(CHCF3)-(CH2)7-、-(CH2)5- (CHCF3)-(CH2)2-、-(CH2)5-(CHCF3)-(CH2)3-、-(CH2)5-(CHCF3)-(CH2)4-、-(CH2)5-(CHCF3)-(CH2)6-、-(CH2)6-(CHCF3)-(CH2)2-、-(CH2)6-(CHCF3)-(CH2)3-、-(CH2)6-(CHCF3)-(CH2)4-、-(CH2)6-(CHCF3)-(CH2)5-、

[0282] -(CHCF3)2-(CH2)-、-(CH2)-(CHCF3)2-、-(CH2)-(CHCF3)2-(CH2)-、-(CH2)-(CHCF3)2-(CH2)2-、-(CH2)-(CHCF3)2-(CH2)3-、-(CH2)-(CHCF3)2-(CH2)4-、-(CH2)-(CHCF3)2-(CH2)5-、-(CH2)-(CHCF3)2-(CH2)6-、-(CH2)-(CHCF3)2-(CH2)7-、-(CH2)-(CHCF3)2-(CH2)8-、-(CH2)-(CHCF3)2-(CH2)9 (CH2)2-(CHCF3)2-(CH2)-、-(CH2)3-(CHCF3)2-(CH2)-、-(CH2)4-(CHCF3)2-(CH2)- CH2)7-(CHCF3)2-(CH2)-、-(CH2)8-(CHCF3)2-(CH2)-、-(CH2)9-(CHCF3)2-(CH2)-、-(CH2)2-(CHCF3)2-(CH2)2-、-(CH2)3-(CHCF3)2-(CH2)3-、-(CH 2)4-(CHCF3)2-(CH2)4-、-(CH2)5-(CHCF3)2-(CH2)5-、-(CH2)2-(CHCF3)2-(CH2)3-、-(CH2)2-(CHCF3)2-(CH2)4-、-(CH2)2-(CHCF3)2-(CH2)5-、-(CH2)2-(CHCF3)2-(CH2)6-、-(CH2)2-(CHCF3)2-(CH2)7-、-(CH2)2-(CHCF3)2-(CH2)8-、-(CH2)3-(CHCF3)2-(CH2)2-、-(CH2)3-(CHCF3)2-(CH2)4-、-( CH2)3-(CHCF3)2-(CH2)5-、-(CH2)3-(CHCF3)2-(CH2)6-、-(CH2)3-(CHCF3)2-(CH2)7-、-(CH2)4-(CHCF3)2-(CH2)2-、-(CH2)4-(CHCF3)2-(CH2)3-、-(CH2)4-(CHCF3)2-(CH2)5-、-(CH2)4-(CHCF3)2-(CH2)6-、-(CH2)5-(CHCF3)2-(CH2)2-、-(CH2)5-(CHCF3)2-(CH2)3-、-(CH2)5-(CHCF3)2-(CH2)4-、-(CH2)6-(CHCF3)2-(CH2)2-、-(CH2)6-(CHCF3)2-(CH2)3-、-(CH2)6-(CHCF3)2-(CH2)4-、

[0283] -(CHCF3)3-(CH2)-、-(CH2)-(CHCF3)3-、-(CH2)-(CHCF3)3-(CH2)-、-(CH2)-(CHCF3)3-(CH2)2-、-(CH2)-(CHCF3)3-(CH2)3-、-(CH2)-(CHCF3)3-(CH2)4-、-(CH2)-(CHCF3)3-(CH2)5-、-(CH2)-(CHCF3)3-(CH2)6-、-(CH2)-(CHCF3)3-(CH2)7-、-(CH2)-(CHCF3)3-(CH2)8 -、-(CH2)2-(CHCF3)3-(CH2)-、-(CH2)3-(CHCF3)3-(CH2)-、-(CH2)4-(CHCF3)3-(CH2)-、-(CH2)5-(CHCF3)3-(CH2)-、-(CH2)6-(CHCF3)3-(CH2)-、-(CH2)7-(CHCF3)3-(CH2)-、-(CH2)8-(CHCF3)3-(CH2)-、-(CH2)2-(CHCF3)3-(CH2)2-、-(CH2)3-(CHCF3)3-(CH2)3-、-(C H2)4-(CHCF3)3-(CH2)4-、-(CH2)2-(CHCF3)3-(CH2)3-、-(CH2)2-(CHCF3)3-(CH2)4-、-(CH2)2-(CHCF3)3-(CH2)5-、-(CH2)2-(CHCF3)3-(CH2)6-、-(CH2)2-(CHCF3)3-(CH2)7-、-(CH2)3-(CHCF3)3-(CH2)2-、-(CH2)3-(CHCF3)3-(CH2)4-、-(CH2)3-(CHCF3)3-(CH2)5-、- (CH2)3-(CHCF3)3-(CH2)6-、-(CH2)4-(CHCF3)3-(CH2)2-、-(CH2)4-(CHCF3)3-(CH2)3-、-(CH2)4-(CHCF3)3-(CH2)5-、-(CH2)5-(CHCF3)3-(CH2)2-、-(CH2)5-(CHCF3)3-(CH2)3-、-(CH2)5-(CHCF3)3-(CH2)4-、-(CH2)6-(CHCF3)3-(CH2)2-、-(CH2)6-(CHCF3)3-(CH2)3-、

[0284] -(CHCF3)4-(CH2)-、-(CH2)-(CHCF3)4-、-(CH2)-(CHCF3)4-(CH2)-、-(CH2)-(CHCF3)4-(CH2)2-、-(CH2)-(CHCF3)4-(CH2)3-、-(CH2)-(CHCF3)4-(CH2)4-、-(CH2)-(CHCF3)4-(CH2)5-、-(CH2)-(CHCF3)4-(CH2)6-、-(CH2)-(CHCF3)4-(CH2)7-、-(CH2)-(CHCF3)4-(CH2)8-、-(CH2)-(CHCF3)4-(CH2)9-、-(CH2)-(CHCF3)4-(CH2) 10 -、-(CH2)2-(CHCF3)4-(CH2)-、-(CH2)3-(CHCF3)4-(CH2)-、-(CH2)4-(CHCF3)4-(CH2)-、-(CH2)5-(CHCF3)4-(CH2)-、-(CH2)6-(CHCF3)4-(CH2)-、-(CH2)7-(CHCF3)4-(CH2)-、-(CH2)2-(CHCF3)4-(CH2)2-、-(CH2)3-(CHCF3)4-(CH2)3-、-(CH2)4-(CHCF3)4-(CH2)4-、-(CH2)5-(CHCF3)4-(CH2)5-、-(CH2)2-(CHCF3 )4-(CH2)3-、-(CH2)2-(CHCF3)4-(CH2)4-、-(CH2)2-(CHCF3)4-(CH2)5-、-(CH2)2-(CHCF3)4-(CH2)6-、-(CH2)3-(CHCF3)4-(CH2)2-、-(CH2)3-(CHCF3)4-(CH2)4-、-(CH2)4-(CHCF3)4-(CH2)2-、-(CH2)4-(CHCF3)4-(CH2)3-、-(CH2)5-(CHCF3)4-(CH2)2-、-(CH2)5-(CHCF3)4-(CH2)3-、-(CH2)6-(CHCF3)4-(CH2)2-、

[0285] -(CHCF3)5-(CH2)-、-(CH2)-(CHCF3)5-、-(CH2)-(CHCF3)5-(CH2)-、-(CH2)-(CHCF3)5-(CH2)2-、-(CH2)-(CHCF3)5-(CH2)3-、-(CH2)-(CHCF3)5-(CH2)4-、-(CH2)-(CHCF3)5-(CH2 )5-、-(CH2)-(CHCF3)5-(CH2)6-、-(CH2)2-(CHCF3)5-(CH2)-、-(CH2)3-(CHCF3)5-(CH2)-、-(CH2)4-(CHCF3)5-(CH2)-、-(CH2)5-(CHCF3)5-(CH2)-、-(CH2)6-(CHCF3)5-(CH2)-、- (CH2)2-(CHCF3)5-(CH2)2-、-(CH2)3-(CHCF3)5-(CH2)3-、-(CH2)4-(CHCF3)5-(CH2)4-、-(CH2)2-(CHCF3)5-(CH2)3-、-(CH2)2-(CHCF3)5-(CH2)4-、-(CH2)2-(CHCF3)5-(CH2)5-、 -(CH2)2-(CHCF3)5-(CH2)6-、-(CH2)3-(CHCF3)5-(CH2)2-、-(CH2)3-(CHCF3)5-(CH2)4-、-(CH2)4-(CHCF3)5-(CH2)2-、-(CH2)4-(CHCF3)5-(CH2)3-、-(CH2)5-(CHCF3)5-(CH2)2-、

[0286] -[C(CH3)CF3]-(CH2)-、-(CH2)-[C(CH3)CF3]-、-(CH2)-[C(CH3)CF3]-(CH2)-、-(CH2)-[C( CH3)CF3]-(CH2)2-、-(CH2)-[C(CH3)CF3]-(CH2)3-、-(CH2)-[C(CH3)CF3]-(CH2)4-、-(CH2) -[C(CH3)CF3]-(CH2)5-、-(CH2)-[C(CH3)CF3]-(CH2)6-、-(CH2)-[C(CH3)CF3]-(CH2)7-、- (CH2)-[C(CH3)CF3]-(CH2)8-、-(CH2)-[C(CH3)CF3]-(CH2)9-、-(CH2)-[C(CH3)CF3]-(CH2) 10-、-(CH2)2-[C(CH3)CF3]-(CH2)-、-(CH2)3-[C(CH3)CF3]-(CH2)-、-(CH2)4-[C(CH3)CF3]-(CH2)-、-(CH2)5-[C(CH3)CF3]-(CH2)-、-(CH2)6-[C(CH3)CF3]-(CH2)-、-(CH2)7-[C(CH3)CF3]-(CH2)-、-(CH2)8-[C(CH3)CF3]-(CH2)-、-(CH2)9-[C(CH3)CF3]-(CH2)-、-(CH2) 10-[C(CH3)CF3]-(CH2)-、-(CH2)2-[C(CH3)CF3]-(CH2)2-、-(CH2)3-[C(CH3)CF3]-(CH2)3-、-(CH2)4-[C(CH3)CF3]-(CH2)4-、-(CH2)5-[C(CH3)CF3]-(CH2)5-、-(CH2)2-[C(CH3)CF3]-(CH2)3-、-(CH2)2-[C(CH3)CF3]-(CH2)4-、-(CH2)2-[C(CH3)CF3]-(CH2)5-、-(CH2)2-[C(CH3)CF3]-(CH2)6-、-(CH2)2-[C(CH3)CF3]-(CH2)7-、-(CH2)2-[C(CH3)CF3]-(CH2)8-、-(CH2)2-[C(CH3)CF3]-(CH2)9-、-(CH2)3-[C(CH3)CF3]-(CH2)2-、-(CH2)3-[C(CH3)CF3]-(CH2)4-、-(CH2)3-[C(CH3)CF3]-(CH2)5-、-(CH2)3-[C(CH3)CF3]-(CH2)6-、-(CH2)3-[C(CH3)CF3]-(CH2)7-、-(CH2)3-[C(CH3)CF3]-(CH2)8-、-(CH2)4-[C(CH3)CF3]-(CH2)2-、-(CH2)4-[C(CH3)CF3]-(CH2)3-、-(CH2)4-[C(CH3)CF3]-(CH2)5-、-(CH2)4-[C(CH3)CF3]-(CH2)6-、-(CH2)4-[C(CH3)CF3]-(CH2)7-、-(CH2)5-[C(CH3)CF3]-(CH2)2-、-(CH2)5-[C(CH3)CF3]-(CH2)3-、-(CH2)5-[C(CH3)CF3]-(CH2)4-、-(CH2)5-[C(CH3)CF3]-(CH2)6-、-(CH2)6-[C(CH3)CF3]-(CH2)2-、-(CH2)6-[C(CH3)CF3]-(CH2)3-、-(CH2)6-[C(CH3)CF3]-(CH2)4-、-(CH2)6-[C(CH3)CF3]-(CH2)5-、

[0287] -[C(CH3)CF3]2-(CH2)-、-(CH2)-[C(CH3)CF3]2-、-(CH2)-[C(CH3)CF3]2-(CH2)-、-(CH2)-[C(CH3)CF3]2-(CH2)2-、-(CH2)-[C(CH3)CF3]2-(CH2)3-、-(CH2)-[C(CH3)CF3]2-(CH2)4-、-(CH2)-[C(CH3)CF3]2-(CH2)5-、-(CH2)-[C(CH3)CF3]2-(CH2)6-、-(CH2)-[C(CH3)CF3]2-(CH2)7-、-(CH2)-[C(CH3)CF3]2-(CH2)8-、-(CH2)-[C(CH3)CF3]2-(CH2)9-、-(CH2)2-[C(CH3)CF3]2-(CH2)-、-(CH2)3-[C(CH3)CF3]2-(CH2)-、-(CH2)4-[C(CH3)CF3]2-(CH2)-、-(CH2)5-[C(CH3)CF3]2-(CH2)-、-(CH2)6-[C(CH3)CF3]2-(CH2)-、-(CH2)7-[C(CH3)CF3]2-(CH2)-、-(CH2)8-[C(CH3)CF3]2-(CH2)-、-(CH2)9-[C(CH3)CF3]2-(CH2)-、-(CH2)2-[C(CH3)CF3]2-(CH2)2-、-(CH2)3-[C(CH3)CF3]2-(CH2)3-、-(CH2)4-[C(CH3)CF3]2-(CH2)4-、-(CH2)5-[C(CH3)CF3]2-(CH2)5-、-(CH2)2-[C(CH3)CF3]2-(CH2)3-、-(CH2)2-[C(CH3)CF3]2-(CH2)4-、-(CH2)2-[C(CH3)CF3]2-(CH2)5-、-(CH2)2-[C(CH3)CF3]2-(CH2)6-、-(CH2)2-[C(CH3)CF3]2-(CH2)7-、-(CH2)2-[C(CH3)CF3]2-(CH2)8-、-(CH2)3-[C(CH3)CF3]2-(CH2)2-、-(CH2)3-[C(CH3)CF3]2-(CH2)4-、-(CH2)3-[C(CH3)CF3]2-(CH2)5-、-(CH2)3-[C(CH3)CF3]2-(CH2)6-、-(CH2)3-[C(CH3)CF3]2-(CH2)7-、-(CH2)4-[C(CH3)CF3]2-(CH2)2-、-(CH2)4-[C(CH3)CF3]2-(CH2)3-、-(CH2)4-[C(CH3)CF3]2-(CH2)5-、-(CH2)4-[C(CH3)CF3]2-(CH2)6-、-(CH2)5-[C(CH3)CF3]2-(CH2)2-、-(CH2)5-[C(CH3)CF3]2-(CH2)3-、-(CH2)5-[C(CH3)CF3]2-(CH2)4-、-(CH2)6-[C(CH3)CF3]2-(CH2)2-、-(CH2)6-[C(CH3)CF3]2-(CH2)3-、-(CH2)6-[C(CH3)CF3]2-(CH2)4-、

[0288] -[C(CH3)CF3]3-(CH2)-、-(CH2)-[C(CH3)CF3]3-、-(CH2)-[C(CH3)CF3]3-(CH2)-、-(CH2)-[C(CH3)CF3]3-(CH2)2-、-(CH2)-[C(CH3)CF3]3-(CH2)3-、-(CH2)-[C(CH3)CF3]3-(CH2)4-、-(CH2)-[C(CH3)CF3]3-(CH2)5-、-(CH2)-[C(CH3)CF3]3-(CH2)6-、-(CH2)-[C(CH3)CF3]3-(CH2)7-、-(CH2)-[C(CH3)CF3]3-(CH2)8-、-(CH2)2-[C(CH3)CF3]3-(CH2)-、-(CH2)3-[C(CH3)CF3]3-(CH2)-、-(CH2)4-[C(CH3)CF3]3-(CH2)-、-(CH2)5-[C(CH3)CF3]3-(CH2)-、-(CH2)6-[C(CH3)CF3]3-(CH2)-、-(CH2)7-[C(CH3)CF3]3-(CH2)-、-(CH2)8-[C(CH3)CF3]3-(CH2)-、-(CH2)2-[C(CH3)CF3]3-(CH2)2-、-(CH2)3-[C(CH3)CF3]3-(CH2)3-、-(CH2)4-[C(CH3)CF3]3-(CH2)4-、-(CH2)2-[C(CH3)CF3]3-(CH2)3-、-(CH2)2-[C(CH3)CF3]3-(CH2)4-、-(CH2)2-[C(CH3)CF3]3-(CH2)5-、-(CH2)2-[C(CH3)CF3]3-(CH2)6-、-(CH2)2-[C(CH3)CF3]3-(CH2)7-、-(CH2)3-[C(CH3)CF3]3-(CH2)2-、-(CH2)3-[C(CH3)CF3]3-(CH2)4-、-(CH2)3-[C(CH3)CF3]3-(CH2)5-、-(CH2)3-[C(CH3)CF3]3-(CH2)6-、-(CH2)4-[C(CH3)CF3]3-(CH2)2-、-(CH2)4-[C(CH3)CF3]3-(CH2)3-、-(CH2)4-[C(CH3)CF3]3-(CH2)5-、-(CH2)5-[C(CH3)CF3]3-(CH2)2-、-(CH2)5-[C(CH3)CF3]3-(CH2)3-、-(CH2)5-[C(CH3)CF3]3-(CH2)4-、-(CH2)6-[C(CH3)CF3]3-(CH2)2-、-(CH2)6-[C(CH3)CF3]3-(CH2)3-、

[0289] -[C(CH3)CF3]4-(CH2)-、-(CH2)-[C(CH3)CF3]4-、-(CH2)-[C(CH3)CF3]4-(CH2)-、-(CH2)-[C(CH3)CF3]4-(CH2)2-、-(CH2)-[C(CH3)CF3]4-(CH2)3-、-(CH2)-[C(CH3)CF3]4-(CH2)4-、-(CH2)-[C(CH3)CF3]4-(CH2)5-、-(CH2)-[C(CH3)CF3]4-(CH2)6-、-(CH2)-[C(CH3)CF3]4-(CH2)7-、-(CH2)-[C(CH3)CF3]4-(CH2)8-、-(CH2)-[C(CH3)CF3]4-(CH2)9-、-(CH2)-[C(CH3)CF3]4-(CH2) 10-、-(CH2)2-[C(CH3)CF3]4-(CH2)-、-(CH2)3-[C(CH3)CF3]4-(CH2)-、-(CH2)4-[C(CH3)CF3]4-(CH2)-、-(CH2)5-[C(CH3)CF3]4-(CH2)-、-(CH2)6-[C(CH3)CF3]4-(CH2)-、-(CH2)7-[C(CH3)CF3]4-(CH2)-、-(CH2)2-[C(CH3)CF3]4-(CH2)2-、-(CH2)3-[C(CH3)CF3]4-(CH2)3-、-(CH2)4-[C(CH3)CF3]4-(CH2)4-、-(CH2)5-[C(CH3)CF3]4-(CH2)5-、-(CH2)2-[C(CH3)CF3]4-(CH2)3-、-(CH2)2-[C(CH3)CF3]4-(CH2)4-、-(CH2)2-[C(CH3)CF3]4-(CH2)5-、-(CH2)2-[C(CH3)CF3]4-(CH2)6-、-(CH2)3-[C(CH3)CF3]4-(CH2)2-、-(CH2)3-[C(CH3)CF3]4-(CH2)4-、-(CH2)4-[C(CH3)CF3]4-(CH2)2-、-(CH2)4-[C(CH3)CF3]4-(CH2)3-、-(CH2)5-[C(CH3)CF3]4-(CH2)2-、-(CH2)5-[C(CH3)CF3]4-(CH2)3-、-(CH2)6-[C(CH3)CF3]4-(CH2)2-、

[0290] -[C(CH3)CF3]5-(CH2)-、-(CH2)-[C(CH3)CF3]5-、-(CH2)-[C(CH3)CF3]5-(CH2)-、-(CH2)-[C(CH3)CF3]5-(CH2)2-、-(CH2)-[C(CH3)CF3]5-(CH2)3-、-(CH2)-[C(CH3)CF3]5-(CH2)4-、-(CH2)-[C(CH3)CF3]5-(CH2)5-、-(CH2)-[C(CH3)CF3]5-(CH2)6-、-(CH2)2-[C(CH3)CF3]5-(CH2)-、-(CH2)3-[C(CH3)CF3]5-(CH2)-、-(CH2)4-[C(CH3)CF3]5-(CH2)-、-(CH2)5-[C(CH3)CF3]5-(CH2)-、-(CH2)6-[C(CH3)CF3]5-(CH2)-、-(CH2)2-[C(CH3)CF3]5-(CH2)2-、-(CH2)3-[C(CH3)CF3]5-(CH2)3-、-(CH2)4-[C(CH3)CF3]5-(CH2)4-、-(CH2)2-[C(CH3)CF3]5-(CH2)3-、-(CH2)2-[C(CH3)CF3]5-(CH2)4-、-(CH2)2-[C(CH3)CF3]5-(CH2)5-、-(CH2)2-[C(CH3)CF3]5-(CH2)6-、-(CH2)3-[C(CH3)CF3]5-(CH2)2-、-(CH2)3-[C(CH3)CF3]5-(CH2)4-、-(CH2)4-[C(CH3)CF3]5-(CH2)2-、-(CH2)4-[C(CH3)CF3]5-(CH2)3-、-(CH2)5-[C(CH3)CF3]5-(CH2)2-、

[0291] -[CH(CH2CF3)]-(CH2)-、-(CH2)-[CH(CH2CF3)]-、-(CH2)-[CH(CH2CF3)]-(CH2)-、-(CH2)-[CH(CH2CF3)]-(CH2)2-、-(CH2)-[CH(CH2CF3)]-(CH2)3-、-(CH2)-[CH(CH2CF3)]-(CH2)4-、-(CH2)-[CH(CH2CF3)]-(CH2)5-、-(CH2)-[CH(CH2CF3)]-(CH2)6-、-(CH2)-[CH(CH2CF3)]-(CH2)7-、-(CH2)-[CH(CH2CF3)]-(CH2)8-、-(CH2)-[CH(CH2CF3)]-(CH2)9-、-(CH2)-[CH(CH2CF3)]-(CH2) 10 -、-(CH2)2-[CH(CH2CF3)]-(CH2)-、-(CH2)3-[CH(CH2CF3)]-(CH2)-、-(CH2)4-[CH(CH2CF3)]-(CH2)-、-(CH2)5-[CH(CH2CF3)]-(CH2)-、-(CH2)6-[CH(CH2CF3)]-(CH2)-、-(CH2)7-[CH(CH2CF3)]-(CH2)-、-(CH2)8-[CH(CH2CF3)]-(CH2)-、-(CH2)9-[CH(CH2CF3)]-(CH2)-、-(CH2) 10-[CH(CH2CF3)]-(CH2)-、-(CH2)2-[CH(CH2CF3)]-(CH2)2-、-(CH2)3-[CH(CH2CF3)]-(CH2)3-、-(CH2)4-[CH(CH2CF3)]-(CH2)4-、-(CH2)5-[CH(CH2CF3)]-(CH2)5-、-(CH2)2-[CH(CH2CF3)]-(CH2)3-、-(CH2)2-[CH(CH2CF3)]-(CH2)4-、-(CH2)2-[CH(CH2CF3)]-(CH2)5-、-(CH2)2-[CH(CH2CF3)]-(CH2)6-、-(CH2)2-[CH(CH2CF3)]-(CH2)7-、-(CH2)2-[CH(CH2CF3)]-(CH2)8-、-(CH2)2-[CH(CH2CF3)]-(CH2)9-、-(CH2)3-[CH(CH2CF3)]-(CH2)2-、-(CH2)3-[CH(CH2CF3)]-(CH2)4-、-(CH2)3-[CH(CH2CF3)]-(CH2)5-、-(CH2)3-[CH(CH2CF3)]-(CH2)6-、-(CH2)3-[CH(CH2CF3)]-(CH2)7-、-(CH2)3-[CH(CH2CF3)]-(CH2)8-、-(CH2)4-[CH(CH2CF3)]-(CH2)2-、-(CH2)4-[CH(CH2CF3)]-(CH2)3-、-(CH2)4-[CH(CH2CF3)]-(CH2)5-、-(CH2)4-[CH(CH2CF3)]-(CH2)6-、-(CH2)4-[CH(CH2CF3)]-(CH2)7-、-(CH2)5-[CH(CH2CF3)]-(CH2)2-、-(CH2)5-[CH(CH2CF3)]-(CH2)3-、-(CH2)5-[CH(CH2CF3)]-(CH2)4-、-(CH2)5-[CH(CH2CF3)]-(CH2)6-、-(CH2)6-[CH(CH2CF3)]-(CH2)2-、-(CH2)6-[CH(CH2CF3)]-(CH2)3-、-(CH2)6-[CH(CH2CF3)]-(CH2)4-、-(CH2)6-[CH(CH2CF3)]-(CH2)5-、

[0292] -[CH(CH2CF3)]2-(CH2)-、-(CH2)-[CH(CH2CF3)]2-、-(CH2)-[CH(CH2CF3)]2-(CH2)-、-(CH2)-[CH(CH2CF3)]2-(CH2)2-、-(CH2)-[CH(CH2CF3)]2-(CH2)3-、-(CH2)-[CH(CH2CF3)]2-(CH2)4-、-(CH2)-[CH(CH2CF3)]2-(CH2)5-、-(CH2)-[CH(CH2CF3)]2-(CH2)6-、-(CH2)-[CH(CH2CF3)]2-(CH2)7-、-(CH2)-[CH(CH2CF3)]2-(CH2)8-、-(CH2)-[CH(CH2CF3)]2-(CH2)9-、-(CH2)2-[CH(CH2CF3)]2-(CH2)-、-(CH2)3-[CH(CH2CF3)]2-(CH2)-、-(CH2)4-[CH(CH2CF3)]2-(CH2)-、-(CH2)5-[CH(CH2CF3)]2-(CH2)-、-(CH2)6-[CH(CH2CF3)]2-(CH2)-、-(CH2)7-[CH(CH2CF3)]2-(CH2)-、-(CH2)8-[CH(CH2CF3)]2-(CH2)-、-(CH2)9-[CH(CH2CF3)]2-(CH2)-、-(CH2)2-[CH(CH2CF3)]2-(CH2)2-、-(CH2)3-[CH(CH2CF3)]2-(CH2)3-、-(CH2)4-[CH(CH2CF3)]2-(CH2)4-、-(CH2)5-[CH(CH2CF3)]2-(CH2)5-、-(CH2)2-[CH(CH2CF3)]2-(CH2)3-、-(CH2)2-[CH(CH2CF3)]2-(CH2)4-、-(CH2)2-[CH(CH2CF3)]2-(CH2)5-、-(CH2)2-[CH(CH2CF3)]2-(CH2)6-、-(CH2)2-[CH(CH2CF3)]2-(CH2)7-、-(CH2)2-[CH(CH2CF3)]2-(CH2)8-、-(CH2)3-[CH(CH2CF3)]2-(CH2)2-、-(CH2)3-[CH(CH2CF3)]2-(CH2)4-、-(CH2)3-[CH(CH2CF3)]2-(CH2)5-、-(CH2)3-[CH(CH2CF3)]2-(CH2)6-、-(CH2)3-[CH(CH2CF3)]2-(CH2)7-、-(CH2)4-[CH(CH2CF3)]2-(CH2)2-、-(CH2)4-[CH(CH2CF3)]2-(CH2)3-、-(CH2)4-[CH(CH2CF3)]2-(CH2)5-、-(CH2)4-[CH(CH2CF3)]2-(CH2)6-、-(CH2)5-[CH(CH2CF3)]2-(CH2)2-、-(CH2)5-[CH(CH2CF3)]2-(CH2)3-、-(CH2)5-[CH(CH2CF3)]2-(CH2)4-、-(CH2)6-[CH(CH2CF3)]2-(CH2)2-、-(CH2)6-[CH(CH2CF3)]2-(CH2)3-、-(CH2)6-[CH(CH2CF3)]2-(CH2)4-、

[0293] -[CH(CH2CF3)]3-(CH2)-、-(CH2)-[CH(CH2CF3)]3-、-(CH2)-[CH(CH2CF3)]3-(CH2)-、-(CH2)-[CH(CH2CF3)]3-(CH2)2-、-(CH2)-[CH(CH2CF3)]3-(CH2)3-、-(CH2)-[CH(CH2CF3)]3-(CH2)4-、-(CH2)-[CH(CH2CF3)]3-(CH2)5-、-(CH2)-[CH(CH2CF3)]3-(CH2)6-、-(CH2)-[CH(CH2CF3)]3-(CH2)7-、-(CH2)-[CH(CH2CF3)]3-(CH2)8-、-(CH2)2-[CH(CH2CF3)]3-(CH2)-、-(CH2)3-[CH(CH2CF3)]3-(CH2)-、-(CH2)4-[CH(CH2CF3)]3-(CH2)-、-(CH2)5-[CH(CH2CF3)]3-(CH2)-、-(CH2)6-[CH(CH2CF3)]3-(CH2)-、-(CH2)7-[CH(CH2CF3)]3-(CH2)-、-(CH2)8-[CH(CH2CF3)]3-(CH2)-、-(CH2)2-[CH(CH2CF3)]3-(CH2)2-、-(CH2)3-[CH(CH2CF3)]3-(CH2)3-、-(CH2)4-[CH(CH2CF3)]3-(CH2)4-、-(CH2)2-[CH(CH2CF3)]3-(CH2)3-、-(CH2)2-[CH(CH2CF3)]3-(CH2)4-、-(CH2)2-[CH(CH2CF3)]3-(CH2)5-、-(CH2)2-[CH(CH2CF3)]3-(CH2)6-、-(CH2)2-[CH(CH2CF3)]3-(CH2)7-、-(CH2)3-[CH(CH2CF3)]3-(CH2)2-、-(CH2)3-[CH(CH2CF3)]3-(CH2)4-、-(CH2)3-[CH(CH2CF3)]3-(CH2)5-、-(CH2)3-[CH(CH2CF3)]3-(CH2)6-、-(CH2)4-[CH(CH2CF3)]3-(CH2)2-、-(CH2)4-[CH(CH2CF3)]3-(CH2)3-、-(CH2)4-[CH(CH2CF3)]3-(CH2)5-、-(CH2)5-[CH(CH2CF3)]3-(CH2)2-、-(CH2)5-[CH(CH2CF3)]3-(CH2)3-、-(CH2)5-[CH(CH2CF3)]3-(CH2)4-、-(CH2)6-[CH(CH2CF3)]3-(CH2)2-、-(CH2)6-[CH(CH2CF3)]3-(CH2)3-、

[0294] -[CH(CH2CF3)]4-(CH2)-、-(CH2)-[CH(CH2CF3)]4-、-(CH2)-[CH(CH2CF3)]4-(CH2)-、-(CH2)-[CH(CH2CF3)]4-(CH2)2-、-(CH2)-[CH(CH2CF3)]4-(CH2)3-、-(CH2)-[CH(CH2CF3)]4-(CH2)4-、-(CH2)-[CH(CH2CF3)]4-(CH2)5-、-(CH2)-[CH(CH2CF3)]4-(CH2)6-、-(CH2)-[CH(CH2CF3)]4-(CH2)7-、-(CH2)-[CH(CH2CF3)]4-(CH2)8-、-(CH2)-[CH(CH2CF3)]4-(CH2)9-、-(CH2)-[CH(CH2CF3)]4-(CH2) 10-、-(CH2)2-[CH(CH2CF3)]4-(CH2)-、-(CH2)3-[CH(CH2CF3)]4-(CH2)-、-(CH2)4-[CH(CH2CF3)]4-(CH2)-、-(CH2)5-[CH(CH2CF3)]4-(CH2)-、-(CH2)6-[CH(CH2CF3)]4-(CH2)-、-(CH2)7-[CH(CH2CF3)]4-(CH2)-、-(CH2)2-[CH(CH2CF3)]4-(CH2)2-、-(CH2)3-[CH(CH2CF3)]4-(CH2)3-、-(CH2)4-[CH(CH2CF3)]4-(CH2)4-、-(CH2)5-[CH(CH2CF3)]4-(CH2)5-、-(CH2)2-[CH(CH2CF3)]4-(CH2)3-、-(CH2)2-[CH(CH2CF3)]4-(CH2)4-、-(CH2)2-[CH(CH2CF3)]4-(CH2)5-、-(CH2)2-[CH(CH2CF3)]4-(CH2)6-、-(CH2)3-[CH(CH2CF3)]4-(CH2)2-、-(CH2)3-[CH(CH2CF3)]4-(CH2)4-、-(CH2)4-[CH(CH2CF3)]4-(CH2)2-、-(CH2)4-[CH(CH2CF3)]4-(CH2)3-、-(CH2)5-[CH(CH2CF3)]4-(CH2)2-、-(CH2)5-[CH(CH2CF3)]4-(CH2)3-、-(CH2)6-[CH(CH2CF3)]4-(CH2)2-、

[0295] -[CH(CH2CF3)]5-(CH2)-、-(CH2)-[CH(CH2CF3)5-、-(CH2)-[CH(CH2CF3)]5-(CH2)-、-(CH2)-[CH(CH2CF3)]5-(CH2)2-、-(CH2)-[CH(CH2CF3)]5-(CH2)3-、-(CH2)-[CH(CH2CF3)]5-(CH2)4-、-(CH2)-[CH(CH2CF3)]5-(CH2)5-、-(CH2)-[CH(CH2CF3)]5-(CH2)6-、-(CH2)2-[CH(CH2CF3)]5-(CH2)-、-(CH2)3-[CH(CH2CF3)]5-(CH2)-、-(CH2)4-[CH(CH2CF3)]5-(CH2)-、-(CH2)5-[CH(CH2CF3)]5-(CH2)-、-(CH2)6-[CH(CH2CF3)]5-(CH2)-、-(CH2)2-[CH(CH2CF3)]5-(CH2)2-、-(CH2)3-[CH(CH2CF3)]5-(CH2)3-、-(CH2)4-[CH(CH2CF3)]5-(CH2)4-、-(CH2)2-[CH(CH2CF3)]5-(CH2)3-、-(CH2)2-[CH(CH2CF3)]5-(CH2)4-、-(CH2)2-[CH(CH2CF3)]5-(CH2)5-、-(CH2)2-[CH(CH2CF3)]5-(CH2)6-、-(CH2)3-[CH(CH2CF3)]5-(CH2)2-、-(CH2)3-[CH(CH2CF3)]5-(CH2)4-、-(CH2)4-[CH(CH2CF3)]5-(CH2)2-、-(CH2)4-[CH(CH2CF3)]5-(CH2)3-、-(CH2)5-[CH(CH2CF3)]5-(CH2)2-、

[0296] -[C(CH3)(CH2CF3)]-(CH2)-、-(CH2)-[C(CH3)(CH2CF3)]-、-(CH2)-[C(CH3)(CH2CF3)]-(CH2)-、-(CH2)-[C(CH3)(CH2CF3)]-(CH2)2-、-(CH2)-[C(CH3)(CH2CF3)]-(CH2)3-、-(CH2)-[C(CH3)(CH2CF3)]-(CH2)4-、-(CH2)-[C(CH3)(CH2CF3)]-(CH2)5-、-(CH2)-[C(CH3)(CH2CF3)]-(CH2)6-、-(CH2)-[C(CH3)(CH2CF3)]-(CH2)7-、-(CH2)-[C(CH3)(CH2CF3)]-(CH2)8-、-(CH2)-[C(CH3)(CH2CF3)]-(CH2)9-、-(CH2)-[C(CH3)(CH2CF3)]-(CH2) 10 -、-(CH2)2-[C(CH3)(CH2CF3)]-(CH2)-、-(CH2)3-[C(CH3)(CH2CF3)]-(CH2)-、-(CH2)4-[C(CH3)(CH2CF3)]-(CH2)-、-(CH2)5-[C(CH3)(CH2CF3)]-(CH2)-、-(CH2)6-[C(CH3)(CH2CF3)]-(CH2)-、-(CH2)7-[C(CH3)(CH2CF3)]-(CH2)-、-(CH2)8-[C(CH3)(CH2CF3)]-(CH2)-、-(CH2)9-[C(CH3)(CH2CF3)]-(CH2)-、-(CH2) 10-[C(CH3)(CH2CF3)]-(CH2)-、-(CH2)2-[C(CH3)(CH2CF3)]-(CH2)2-、-(CH2)3-[C(CH3)(CH2CF3)]-(CH2)3-、-(CH2)4-[C(CH3)(CH2CF3)]-(CH2)4-、-(CH2)5-[C(CH3)(CH2CF3)]-(CH2)5-、-(CH2)2-[C(CH3)(CH2CF3)]-(CH2)3-、-(CH2)2-[C(CH3)(CH2CF3)]-(CH2)4-、-(CH2)2-[C(CH3)(CH2CF3)]-(CH2)5-、-(CH2)2-[C(CH3)(CH2CF3)]-(CH2)6-、-(CH2)2-[C(CH3)(CH2CF3)]-(CH2)7-、-(CH2)2-[C(CH3)(CH2CF3)]-(CH2)8-、-(CH2)2-[C(CH3)(CH2CF3)]-(CH2)9-、-(CH2)3-[C(CH3)(CH2CF3)]-(CH2)2-、-(CH2)3-[C(CH3)(CH2CF3)]-(CH2)4-、-(CH2)3-[C(CH3)(CH2CF3)]-(CH2)5-、-(CH2)3-[C(CH3)(CH2CF3)]-(CH2)6-、-(CH2)3-[C(CH3)(CH2CF3)]-(CH2)7-、-(CH2)3-[C(CH3)(CH2CF3)]-(CH2)8-、-(CH2)4-[C(CH3)(CH2CF3)]-(CH2)2-、-(CH2)4-[C(CH3)(CH2CF3)]-(CH2)3-、-(CH2)4-[C(CH3)(CH2CF3)]-(CH2)5-、-(CH2)4-[C(CH3)(CH2CF3)]-(CH2)6-、-(CH2)4-[C(CH3)(CH2CF3)]-(CH2)7-、-(CH2)5-[C(CH3)(CH2CF3)]-(CH2)2-、-(CH2)5-[C(CH3)(CH2CF3)]-(CH2)3-、-(CH2)5-[C(CH3)(CH2CF3)]-(CH2)4-、-(CH2)5-[C(CH3)(CH2CF3)]-(CH2)6-、-(CH2)6-[C(CH3)(CH2CF3)]-(CH2)2-、-(CH2)6-[C(CH3)(CH2CF3)]-(CH2)3-、-(CH2)6-[C(CH3)(CH2CF3)]-(CH2)4-、-(CH2)6-[C(CH3)(CH2CF3)]-(CH2)5-、

[0297] -[C(CH3)(CH2CF3)]2-(CH2)-、-(CH2)-[C(CH3)(CH2CF3)]2-、-(CH2)-[C(CH3)(CH2CF3)]2-(CH2)-、-(CH2)-[C(CH3)(CH2CF3)]2-(CH2)2-、-(CH2)-[C(CH3)(CH2CF3)]2-(CH2)3-、-(CH2)-[C(CH3)(CH2CF3)]2-(CH2)4-、-(CH2)-[C(CH3)(CH2CF3)]2-(CH2)5-、-(CH2)-[C(CH3)(CH2CF3)]2-(CH2)6-、-(CH2)-[C(CH3)(CH2CF3)]2-(CH2)7-、-(CH2)-[C(CH3)(CH2CF3)]2-(CH2)8-、-(CH2)-[C(CH3)(CH2CF3)]2-(CH2)9-、-(CH2)2-[C(CH3)(CH2CF3)]2-(CH2)-、-(CH2)3-[C(CH3)(CH2CF3)]2-(CH2)-、-(CH2)4-[C(CH3)(CH2CF3)]2-(CH2)-、-(CH2)5-[C(CH3)(CH2CF3)]2-(CH2)-、-(CH2)6-[C(CH3)(CH2CF3)]2-(CH2)-、-(CH2)7-[C(CH3)(CH2CF3)]2-(CH2)-、-(CH2)8-[C(CH3)(CH2CF3)]2-(CH2)-、-(CH2)9-[C(CH3)(CH2CF3)]2-(CH2)-、-(CH2)2-[C(CH3)(CH2CF3)]2-(CH2)2-、-(CH2)3-[C(CH3)(CH2CF3)]2-(CH2)3-、-(CH2)4-[C(CH3)(CH2CF3)]2-(CH2)4-、-(CH2)5-[C(CH3)(CH2CF3)]2-(CH2)5-、-(CH2)2-[C(CH3)(CH2CF3)]2-(CH2)3-、-(CH2)2-[C(CH3)(CH2CF3)]2-(CH2)4-、-(CH2)2-[C(CH3)(CH2CF3)]2-(CH2)5-、-(CH2)2-[C(CH3)(CH2CF3)]2-(CH2)6-、-(CH2)2-[C(CH3)(CH2CF3)]2-(CH2)7-、-(CH2)2-[C(CH3)(CH2CF3)]2-(CH2)8-、-(CH2)3-[C(CH3)(CH2CF3)]2-(CH2)2-、-(CH2)3-[C(CH3)(CH2CF3)]2-(CH2)4-、-(CH2)3-[C(CH3)(CH2CF3)]2-(CH2)5-、-(CH2)3-[C(CH3)(CH2CF3)]2-(CH2)6-、-(CH2)3-[C(CH3)(CH2CF3)]2-(CH2)7-、-(CH2)4-[C(CH3)(CH2CF3)]2-(CH2)2-、-(CH2)4-[C(CH3)(CH2CF3)]2-(CH2)3-、-(CH2)4-[C(CH3)(CH2CF3)]2-(CH2)5-、-(CH2)4-[C(CH3)(CH2CF3)]2-(CH2)6-、-(CH2)5-[C(CH3)(CH2CF3)]2-(CH2)2-、-(CH2)5-[C(CH3)(CH2CF3)]2-(CH2)3-、-(CH2)5-[C(CH3)(CH2CF3)]2-(CH2)4-、-(CH2)6-[C(CH3)(CH2CF3)]2-(CH2)2-、-(CH2)6-[C(CH3)(CH2CF3)]2-(CH2)3-、-(CH2)6-[C(CH3)(CH2CF3)]2-(CH2)4-、

[0298] -[C(CH3)(CH2CF3)]3-(CH2)-、-(CH2)-[C(CH3)(CH2CF3)]3-、-(CH2)-[C(CH3)(CH2CF3)]3-(CH2)-、-(CH2)-[C(CH3)(CH2CF3)]3-(CH2)2-、-(CH2)-[C(CH3)(CH2CF3)]3-(CH2)3-、-(CH2)-[C(CH3)(CH2CF3)]3-(CH2)4-、-(CH2)-[C(CH3)(CH2CF3)]3-(CH2)5-、-(CH2)-[C(CH3)(CH2CF3)]3-(CH2)6-、-(CH2)-[C(CH3)(CH2CF3)]3-(CH2)7-、-(CH2)-[C(CH3)(CH2CF3)]3-(CH2)8-、-(CH2)2-[C(CH3)(CH2CF3)]3-(CH2)-、-(CH2)3-[C(CH3)(CH2CF3)]3-(CH2)-、-(CH2)4-[C(CH3)(CH2CF3)]3-(CH2)-、-(CH2)5-[C(CH3)(CH2CF3)]3-(CH2)-、-(CH2)6-[C(CH3)(CH2CF3)]3-(CH2)-、-(CH2)7-[C(CH3)(CH2CF3)]3-(CH2)-、-(CH2)8-[C(CH3)(CH2CF3)]3-(CH2)-、-(CH2)2-[C(CH3)(CH2CF3)]3-(CH2)2-、-(CH2)3-[C(CH3)(CH2CF3)]3-(CH2)3-、-(CH2)4-[C(CH3)(CH2CF3)]3-(CH2)4-、-(CH2)2-[C(CH3)(CH2CF3)]3-(CH2)3-、-(CH2)2-[C(CH3)(CH2CF3)]3-(CH2)4-、-(CH2)2-[C(CH3)(CH2CF3)]3-(CH2)5-、-(CH2)2-[C(CH3)(CH2CF3)]3-(CH2)6-、-(CH2)2-[C(CH3)(CH2CF3)]3-(CH2)7-、-(CH2)3-[C(CH3)(CH2CF3)]3-(CH2)2-、-(CH2)3-[C(CH3)(CH2CF3)]3-(CH2)4-、-(CH2)3-[C(CH3)(CH2CF3)]3-(CH2)5-、-(CH2)3-[C(CH3)(CH2CF3)]3-(CH2)6-、-(CH2)4-[C(CH3)(CH2CF3)]3-(CH2)2-、-(CH2)4-[C(CH3)(CH2CF3)]3-(CH2)3-、-(CH2)4-[C(CH3)(CH2CF3)]3-(CH2)5-、-(CH2)5-[C(CH3)(CH2CF3)]3-(CH2)2-、-(CH2)5-[C(CH3)(CH2CF3)]3-(CH2)3-、-(CH2)5-[C(CH3)(CH2CF3)]3-(CH2)4-、-(CH2)6-[C(CH3)(CH2CF3)]3-(CH2)2-、-(CH2)6-[C(CH3)(CH2CF3)]3-(CH2)3-、

[0299] -[C(CH3)(CH2CF3)]4-(CH2)-、-(CH2)-[C(CH3)(CH2CF3)]4-、-(CH2)-[C(CH3)(CH2CF3)]4-(CH2)-、-(CH2)-[C(CH3)(CH2CF3)]4-(CH2)2-、-(CH2)-[C(CH3)(CH2CF3)]4-(CH2)3-、-(CH2)-[C(CH3)(CH2CF3)]4-(CH2)4-、-(CH2)-[C(CH3)(CH2CF3)]4-(CH2)5-、-(CH2)-[C(CH3)(CH2CF3)]4-(CH2)6-、-(CH2)-[C(CH3)(CH2CF3)]4-(CH2)7-、-(CH2)-[C(CH3)(CH2CF3)]4-(CH2)8-、-(CH2)-[C(CH3)(CH2CF3)]4-(CH2)9-、-(CH2)-[C(CH3)(CH2CF3)]4-(CH2) 10-、-(CH2)2-[C(CH3)(CH2CF3)]4-(CH2)-、-(CH2)3-[C(CH3)(CH2CF3)]4-(CH2)-、-(CH2)4-[C(CH3)(CH2CF3)]4-(CH2)-、-(CH2)5-[C(CH3)(CH2CF3)]4-(CH2)-、-(CH2)6-[C(CH3)(CH2CF3)]4-(CH2)-、-(CH2)7-[C(CH3)(CH2CF3)]4-(CH2)-、-(CH2)2-[C(CH3)(CH2CF3)]4-(CH2)2-、-(CH2)3-[C(CH3)(CH2CF3)]4-(CH2)3-、-(CH2)4-[C(CH3)(CH2CF3)]4-(CH2)4-、-(CH2)5-[C(CH3)(CH2CF3)]4-(CH2)5-、-(CH2)2-[C(CH3)(CH2CF3)]4-(CH2)3-、-(CH2)2-[C(CH3)(CH2CF3)]4-(CH2)4-、-(CH2)2-[C(CH3)(CH2CF3)]4-(CH2)5-、-(CH2)2-[C(CH3)(CH2CF3)]4-(CH2)6-、-(CH2)3-[C(CH3)(CH2CF3)]4-(CH2)2-、-(CH2)3-[C(CH3)(CH2CF3)]4-(CH2)4-、-(CH2)4-[C(CH3)(CH2CF3)]4-(CH2)2-、-(CH2)4-[C(CH3)(CH2CF3)]4-(CH2)3-、-(CH2)5-[C(CH3)(CH2CF3)]4-(CH2)2-、-(CH2)5-[C(CH3)(CH2CF3)]4-(CH2)3-、-(CH2)6-[C(CH3)(CH2CF3)]4-(CH2)2-、

[0300] -[C(CH3)(CH2CF3)]5-(CH2)-、-(CH2)-[C(CH3)(CH2CF3)]5-、-(CH2)-[C(CH3)(CH2CF3)]5-(CH2)-、-(CH2)-[C(CH3)(CH2CF3)]5-(CH2)2-、-(CH2)-[C(CH3)(CH2CF3)]5-(CH2)3-、-(CH2)-[C(CH3)(CH2CF3)]5-(CH2)4-、-(CH2)-[C(CH3)(CH2CF3)]5-(CH2)5-、-(CH2)-[C(CH3)(CH2CF3)]5-(CH2)6-、-(CH2)2-[C(CH3)(CH2CF3)]5-(CH2)-、-(CH2)3-[C(CH3)(CH2CF3)]5-(CH2)-、-(CH2)4-[C(CH3)(CH2CF3)]5-(CH2)-、-(CH2)5-[C(CH3)(CH2CF3)]5-(CH2)-、-(CH2)6-[C(CH3)(CH2CF3)]5-(CH2)-、-(CH2)2-[C(CH3)(CH2CF3)]5-(CH2)2-、-(CH2)3-[C(CH3)(CH2CF3)]5-(CH2)3-、-(CH2)4-[C(CH3)(CH2CF3)]5-(CH2)4-、-(CH2)2-[C(CH3)(CH2CF3)]5-(CH2)3-、-(CH2)2-[C(CH3)(CH2CF3)]5-(CH2)4-、-(CH2)2-[C(CH3)(CH2CF3)]5-(CH2)5-、-(CH2)2-[C(CH3)(CH2CF3)]5-(CH2)6-、-(CH2)3-[C(CH3)(CH2CF3)]5-(CH2)2-、-(CH2)3-[C(CH3)(CH2CF3)]5-(CH2)4-、-(CH2)4-[C(CH3)(CH2CF3)]5-(CH2)2-、-(CH2)4-[C(CH3)(CH2CF3)]5-(CH2)3-、-(CH2)5-[C(CH3)(CH2CF3)]5-(CH2)2-、

[0301] -(CH2)2-(CF2)-O-(CF2)-(CH2)2-、-(CH2)2-(CF2)-O-(CH2)-O-(CF2)-(CH2)2-、-(CH2)2-(CF2)-O-(CH2)2-O-(CF2)-(CH2)2、

[0302] -(CH2)-(CF2)-O-(CF2)-O-(CF2)-(CH2)-、-(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-、-(CH2)3-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-、-(CH2)4-(CF2)-O-(CF2)-O-(CF2)-(CH2)4-、-(CH2)-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-、-(CH2)-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-、-(CH2)-(CF2)-O-(CF2)-O-(CF2)-(CH2)4-、-(CH2)-(CF2)-O-(CF2)-O-(CF2)-(CH2)5-、-(CH2)-(CF2)-O-(CF2)-O-(CF2)-(CH2)6-、-(CH2)-(CF2)-O-(CF2)-O-(CF2)-(CH2)7-、-(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)-、-(CH2)3-(CF2)-O-(CF2)-O-(CF2)-(CH2)-、-(CH2)4-(CF2)-O-(CF2)-O-(CF2)-(CH2)-、-(CH2)5-(CF2)-O-(CF2)-O-(CF2)-(CH2)-、-(CH2)6-(CF2)-O-(CF2)-O-(CF2)-(CH2)-、-(CH2)7-(CF2)-O-(CF2)-O-(CF2)-(CH2)-、-(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-、-(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)4-、-(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)5-、-(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)6-、-(CH2)3-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-、-(CH2)4-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-、-(CH2)5-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-、-(CH2)6-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-、-(CH2)3-(CF2)-O-(CF2)-O-(CF2)-(CH2)4-、-(CH2)4-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-、-(CH2)3-(CF2)-O-(CF2)-O-(CF2)-(CH2)5-、-(CH2)5-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-、

[0303] -(CH2)-(CF2)-O-(CF2)2-O-(CF2)-(CH2)-、-(CH2)2-(CF2)-O-(CF2)2-O-(CF2)-(CH2)2-、-(CH2)3-(CF2)-O-(CF2)2-O-(CF2)-(CH2)3-、-(CH2)4-(CF2)-O-(CF2)2-O-(CF2)-(CH2)4-、-(CH2)-(CF2)-O-(CF2)2-O-(CF2)-(CH2)2-、-(CH2)-(CF2)-O-(CF2)2-O-(CF2)-(CH2)3-、-(CH2)-(CF2)-O-(CF2)2-O-(CF2)-(CH2)4-、-(CH2)-(CF2)-O-(CF2)2-O-(CF2)-(CH2)5-、-(CH2)-(CF2)-O-(CF2)2-O-(CF2)-(CH2)6-、-(CH2)-(CF2)-O-(CF2)2-O-(CF2)-(CH2)7-、-(CH2)2-(CF2)-O-(CF2)2-O-(CF2)-(CH2)-、-(CH2)3-(CF2)-O-(CF2)2-O-(CF2)-(CH2)-、-(CH2)4-(CF2)-O-(CF2)2-O-(CF2)-(CH2)-、-(CH2)5-(CF2)-O-(CF2)2-O-(CF2)-(CH2)-、-(CH2)6-(CF2)-O-(CF2)2-O-(CF2)-(CH2)-、-(CH2)7-(CF2)-O-(CF2)2-O-(CF2)-(CH2)-、-(CH2)2-(CF2)-O-(CF2)2-O-(CF2)-(CH2)3-、-(CH2)2-(CF2)-O-(CF2)2-O-(CF2)-(CH2)4-、-(CH2)2-(CF2)-O-(CF2)2-O-(CF2)-(CH2)5-、-(CH2)2-(CF2)-O-(CF2)2-O-(CF2)-(CH2)6-、-(CH2)3-(CF2)-O-(CF2)2-O-(CF2)-(CH2)2-、-(CH2)4-(CF2)-O-(CF2)2-O-(CF2)-(CH2)2-、-(CH2)5-(CF2)-O-(CF2)2-O-(CF2)-(CH2)2-、-(CH2)6-(CF2)-O-(CF2)2-O-(CF2)-(CH2)2-、-(CH2)3-(CF2)-O-(CF2)2-O-(CF2)-(CH2)4-、-(CH2)4-(CF2)-O-(CF2)2-O-(CF2)-(CH2)3-、-(CH2)3-(CF2)-O-(CF2)2-O-(CF2)-(CH2)5-、-(CH2)5-(CF2)-O-(CF2)2-O-(CF2)-(CH2)3-、

[0304] -(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-、-(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-、-(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-、-(CH2)4-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)4-、-(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-、-(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-、-(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-、-(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)4-、-(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)5-、-(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)6-、-(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)7-、-(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-、-(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-、-(CH2)4-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-、-(CH2)5-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-、-(CH2)6-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-、-(CH2)7-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-、-(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-、-(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)4-、-(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)5-、-(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)6-、-(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-、-(CH2)4-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-、-(CH2)5-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-、-(CH2)6-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-、-(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)4-、-(CH2)4-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-、-(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)5-、-(CH2)5-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-、

[0305] -(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-、-(CH2)2-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-、-(CH2)3-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-、-(CH2)4-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)4-、-(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-、-(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-、-(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)4-、-(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)5-、-(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)6-、-(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)7-、-(CH2)2-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-、-(CH2)3-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-、-(CH2)4-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-、-(CH2)5-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-、-(CH2)6-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-、-(CH2)7-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-、-(CH2)2-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-、-(CH2)2-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)4-、-(CH2)2-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)5-、-(CH2)2-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)6-、-(CH2)3-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-、-(CH2)4-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-、-(CH2)5-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-、-(CH2)6-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-、-(CH2)3-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)4-、-(CH2)4-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-、-(CH2)3-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)5-、-(CH2)5-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-、

[0306] -(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-、-(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-、-(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-、-(CH2)4-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)4-、-(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-、-(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-、-(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)4-、-(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)5-、-(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)6-、-(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)7-、-(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-、-(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-、-(CH2)4-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-、-(CH2)5-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-、-(CH2)6-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-、-(CH2)7-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-、-(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-、-(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)4-、-(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)5-、-(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)6-、-(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-, -(CH2)4-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-, -(CH2)5-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-, -(CH2)6-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-, -(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)4-, -(CH2)4-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-, -(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)5-, -(CH2)5-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-. ,

[0307] According to the present invention, preferred examples of -R2- are -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)9-, and -(CH2) 10 -、-(CH2) 11 -、-(CH2) 12 -、-(CH2) 13-, -(CH2)2-S-(CH2)2-, -(CH2)2-SO2-(CH2)2-, -(CH2)2-S-(CH2)2-S-(CH2)2-, -(CH2)2-O-(CH2)2-O-(CH2)2-, -(CH2)2-S-(CH2)2-O-(CH2)2-, -(CH2)2-SO2-(CH2)2-O-(CH2)2-, -(CH2)2-SO2-(CH2)2-S-(CH2)2-, -(CH2)2-O-(CH2)2-O-(CH2)2-O-(CH2)2-, -(CH2)2-O-(CH2)2-S-(CH2)2-O-(CH2)2-, -(CH2)2-S-(CH2)2-O-(CH2)2-S-(CH2)2-, -(CH2)2-SO2-(CH2)2-O-(CH2)2-SO2-(CH2)2-, -(CH2)2-S-(CH2)2-S-(CH2)2-S-(CH2)2-, -(CH2)2-SO2-(CH2)2-S-(CH2)2-SO2-(CH2)2-, -(CH2)2-SO2-(CH2)2-SO2-(CH2)2-SO2-(CH2)2-, -(CH2)2-O-(CH2)2-SO2-(CH2)2-O-(CH2)2-, -(CH2)3-(CF2)-(CH2)3-, -(CH2)-(CF2)3-(CH2)-, -(CH2)2-(CF2)4-(CH2)2-, -(CH2)-[CH(CF3)]-(CH2)-, -(CH2)-[C(CH3)CF3]-(CH2)-, -(CH2)-[CH(CH2CF3)]-(CH2)-, -(CH2)-[C(CH3)(CH2CF3)]-(CH2)-, -(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)2- and -(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-。

[0308] According to the present invention, particularly preferred examples of -R2- are -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)9-, -(CH2) 10 -, -(CH2) 11 -, -(CH2) 12 -, -(CH2) 13-, -(CH2)2-S-(CH2)2-, -(CH2)2-SO2-(CH2)2-, -(CH2)2-S-(CH2)2-S-(CH2)2-, -( CH2)2-O-(CH2)2-O-(CH2)2-, -(CH2)2-O-(CH2)2-O-(CH2)2-O-(CH2)2-, -(CH2)2-O -(CH2)2-S-(CH2)2-O-(CH2)2-, -(CH2)2-S-(CH2)2-O-(CH2)2-S-(CH2)2-, -(CH2) 2-S-(CH2)2-S-(CH2)2-S-(CH2)2- and -(CH2)2-SO2-(CH2)2-S-(CH2)2-SO2-(CH2)2-.

[0309] If at least one of the substituents -R2- in the connecting element Y-R2- or N-R2-R1 corresponds to –(C(R)2) o –, wherein R and o have the meanings described above or preferably as described above, and compounds of formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) and (I”) having substituents described above or preferably as described above, wherein the substituents have polymerizable groups as described above or preferably as described above or as follows.

[0310] Therefore, if the substituent -R2- in at least one connecting element Y-R2- or N-R2-R1 corresponds to –(C(R)2) o – where R and o have the meanings described above or preferably as described above, monomers of formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), and (I”) having substituents described above or preferably as described above, for the preparation of ophthalmic devices as described above or for the manufacture of precursor articles of ophthalmic devices, are preferred, wherein the substituents have polymerizable groups as described above or preferably as described above or as follows. Such ophthalmic devices and precursor articles prepared using these monomers are particularly preferred.

[0311] According to the present invention, particularly preferred examples of -R2- are -(CH2)8-, -(CH2)9-, and -(CH2) 10 -、-(CH2) 11 - and -(CH2) 12 Very particularly preferably, according to the invention, -R2- is -(CH2). 12 -

[0312] Therefore, the present invention also relates to ophthalmic devices or precursor articles for manufacturing ophthalmic devices, comprising polymeric compounds of formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), and (I”) as described above or preferably as described above, wherein -R2- is independently –(C(R)2) each time it appears. o – where R and o have the meanings described above or preferably as described above.

[0313] Therefore, the present invention relates to compounds of formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), and (I”) as described above or preferably as described above, wherein -R2- is independently –(C(R)2) each time it appears. o – where R and o have the meanings as described above or preferably as described above, and take into account the disclaimers disclosed in this invention.

[0314] The substituent Y-R2- in formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), and (I”) is selected from the group consisting of O-R2-, -R2- (where Y is a bond), SO2-R2-, and S-R2-, wherein -R2- has the meaning as described above or preferably or particularly preferably as described above.

[0315] The substituent Y-R2- is preferably selected from the group consisting of O-R2- and -R2- (where Y is a bond), wherein -R2- has the meaning as described above or preferably or particularly preferably as described above.

[0316] The substituent Y-R2-R1 in formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), and (I”) is selected from the group consisting of O-R2-R1, -R2-R1, SO2-R2-R1, and S-R2-R1, or preferably from the group consisting of O-R2-R1 and -R2-R1, wherein -R2- has the meaning as described above or preferably or particularly preferably as described above, and wherein R1 is trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, or a polymerizable group according to formula (4).

[0317]

[0318] in

[0319] X 11 Choose the groups composed of O, S, O-SO2, SO2-O, C(=O), OC(=O), C(=O)O, S(C=O), and (C=O)S.

[0320] R5, R6, and R7 are each independently selected from the group consisting of H, F, a straight-chain or branched, non-fluorinated, partially or fully fluorinated alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and each time they appear.

[0321] c is 0 or 1.

[0322] The substituents N-R2-R1 in formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), and (I”) are preferred, wherein -R2- has the meaning as described above or preferably as described above, and wherein R1 is trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, or a polymerizable group according to formula (4).

[0323]

[0324] in

[0325] X 11 Choose the groups composed of O, S, O-SO2, SO2-O, C(=O), OC(=O), C(=O)O, S(C=O), and (C=O)S.

[0326] R5, R6, and R7 are each independently selected from the group consisting of H, F, a straight-chain or branched, non-fluorinated, partially or fully fluorinated alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and each time they appear.

[0327] c is 0 or 1.

[0328] In another preferred embodiment of the invention, in compounds of formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), and (I”) that act as precursor articles for the preparation of ophthalmic devices as described above or for the manufacture of ophthalmic devices, or for the preparation of oligomers, polymers, or copolymers according to the invention, or in compounds according to the invention, c, X 11 R5, R6, and R7 have the following preferred meanings:

[0329] Preferably, R6 and R7 are H. Preferably, c is 1.

[0330] Preferably, R5 is H, methyl, ethyl, or phenyl. Particularly preferably, R5 is H or methyl.

[0331] Preferably, X 11 It is C(=O), OC(=O), or C(=O)O. Particularly preferred is X. 11 It is C(=O)O.

[0332] Therefore, the preferred alkenyl group of formula (4) as the polymerizable group R1 according to the present invention is represented by any one of the group consisting of formulas (4-1), (4-2), (4-3), (4-4), (4-5), (4-6), (4-7), (4-8), (4-9), (4-10), (4-11) and (4-12):

[0333]

[0334] The particularly preferred alkenyl group of formula (4) of polymerizable group R1 according to the invention is represented by any one of the group consisting of formulas (4-1), (4-2), (4-3), (4-5), (4-6), (4-11) and (4-12) as described above.

[0335] The alkenyl group represented by formula (4-1) is called a methacrylate. The alkenyl group represented by formula (4-2) is called an acrylate.

[0336] The preferred group R1 is preferably combined with the preferred groups of the linking element -R2- and / or the linking element Y-R2. Combinations in which two O atoms or one O atom and one S atom are directly bonded to each other are excluded, as is known to those skilled in the art of organic chemistry.

[0337] Therefore, the substituent Y-R2-R1 in formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), and (I”) is particularly preferably selected from the group consisting of the following:

[0338] O-(CH2)5-R 1 O-(CH2)6-R 1 O-(CH2)7-R 1 O-(CH2)8-R 1 O-(CH2)9-R 1 O-(CH2) 10 -R 1 O-(CH2) 11 -R 1 O-(CH2) 12 -R 1 O-(CH2) 13 -R 1 O-(CH2)2-S-(CH2)2-R 1 O-(CH2)2-SO2-(CH2)2-R 1 ,O-(CH2)2-S-(CH2)2-S-(CH2)2-R 1 ,O-(CH2)2-O-(CH2)2-O-(CH2)2-R 1 ,O-(CH2)2-S-(CH2)2-O-(CH2)2-R 1 ,O-(CH2)2-SO2-(CH2)2-O-(CH2)2-R 1 ,O-(CH2)2-SO2-(CH2)2-S-(CH2)2-R 1 ,O-(CH2)2-O-(CH2)2-O-(CH2)2-O-(CH2)2-R 1 ,O-(CH2)2-O-(CH2)2-S-(CH2)2-O-(CH2)2-R 1 ,O-(CH2)2-S-(CH2)2-O-(CH2)2-S-(CH2)2-R 1 ,O-(CH2)2-SO2-(CH2)2-O-(CH2)2-SO2-(CH2)2-R 1 ,O-(CH2)2-S-(CH2)2-S-(CH2)2-S-(CH2)2-R 1 ,O-(CH2)2-SO2-(CH2)2-S-(CH2)2-SO2-(CH2)2-R 1,O-(CH2)2-SO2-(CH2)2-SO2-(CH2)2-SO2-(CH2)2-R 1 ,O-(CH2)2-O-(CH2)2-SO2-(CH2)2-O-(CH2)2-R 1 O-(CH2)3-(CF2)-(CH2)3-R 1 O-(CH2)-(CF2)3-(CH2)-R 1 O-(CH2)2-(CF2)4-(CH2)2-R 1 O-(CH2)-[CH(CF3)]-(CH2)-R 1 ,O-(CH2)-[C(CH3)CF3]-(CH2)-R 1 ,O-(CH2)-[CH(CH2CF3)]-(CH2)-R 1 ,O-(CH2)-[C(CH3)(CH2CF3)]-(CH2)-R 1 ,O-(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-R 1 and O-(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-R 1 R1 is selected from the group consisting of alkenyl groups of free formulas (4-1), (4-2), (4-3), (4-4), (4-5), (4-6), (4-7), (4-8), (4-9), (4-10), (4-11), or (4-12);

[0339] -(CH2)5-R 1 -(CH2)6-R 1 -(CH2)7-R 1 -(CH2)8-R 1 -(CH2)9-R 1 -(CH2) 10 -R 1 -(CH2) 11 -R 1 -(CH2) 12 -R 1 -(CH2) 13 -R 1 -(CH2)2-S-(CH2)2-R 1 -(CH2)2-SO2-(CH2)2-R 1 ,-(CH2)2-S-(CH2)2-S-(CH2)2-R 1, -(CH2)2-O-(CH2)2-O-(CH2)2-R 1 , -(CH2)2-S-(CH2)2-O-(CH2)2-R 1 , -(CH2)2-SO2-(CH2)2-O-(CH2)2-R 1 , -(CH2)2-SO2-(CH2)2-S-(CH2)2-R 1 , -(CH2)2-O-(CH2)2-O-(CH2)2-O-(CH2)2-R 1 , -(CH2)2-O-(CH2)2-S-(CH2)2-O-(CH2)2-R 1 , -(CH2)2-S-(CH2)2-O-(CH2)2-S-(CH2)2-R 1 , -(CH2)2-SO2-(CH2)2-O-(CH2)2-SO2-(CH2)2-R 1 , -(CH2)2-S-(CH2)2-S-(CH2)2-S-(CH2)2-R 1 , -(CH2)2-SO2-(CH2)2-S-(CH2)2-SO2-(CH2)2-R 1 , -(CH2)2-SO2-(CH2)2-SO2-(CH2)2-SO2-(CH2)2-R 1 , -(CH2)2-O-(CH2)2-SO2-(CH2)2-O-(CH2)2-R 1 , -(CH2)3-(CF2)-(CH2)3-R 1 , -(CH2)-(CF2)3-(CH2)-R 1 , -(CH2)2-(CF2)4-(CH2)2-R 1 , -(CH2)-[CH(CF3)]-(CH2)-R 1 , -(CH2)-[C(CH3)CF3]-(CH2)-R 1 , -(CH2)-[CH(CH2CF3)]-(CH2)-R 1 , -(CH2)-[C(CH3)(CH2CF3)]-(CH2)-R 1 , -(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-R 1 and -(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-R 1, where Y is a bond, and R1 is selected from the group consisting of alkenyl groups of free formula (4-1), (4-2), (4-3), (4-4), (4-5), (4-6), (4-7), (4-8), (4-9), (4-10), (4-11) or (4-12);

[0340] S-(CH2)5-R 1 S-(CH2)6-R 1 S-(CH2)7-R 1 S-(CH2)8-R 1 S-(CH2)9-R 1 S-(CH2) 10 -R 1 S-(CH2) 11 -R 1 S-(CH2) 12 -R 1 S-(CH2) 13 -R 1 S-(CH2)2-S-(CH2)2-R 1 S-(CH2)2-SO2-(CH2)2-R 1 ,S-(CH2)2-S-(CH2)2-S-(CH2)2-R 1 ,S-(CH2)2-O-(CH2)2-O-(CH2)2-R 1 ,S-(CH2)2-S-(CH2)2-O-(CH2)2-R 1 ,S-(CH2)2-SO2-(CH2)2-O-(CH2)2-R 1 ,S-(CH2)2-SO2-(CH2)2-S-(CH2)2-R 1 ,S-(CH2)2-O-(CH2)2-O-(CH2)2-O-(CH2)2-R 1 ,S-(CH2)2-O-(CH2)2-S-(CH2)2-O-(CH2)2-R 1 ,S-(CH2)2-S-(CH2)2-O-(CH2)2-S-(CH2)2-R 1 ,S-(CH2)2-SO2-(CH2)2-O-(CH2)2-SO2-(CH2)2-R 1 ,S-(CH2)2-S-(CH2)2-S-(CH2)2-S-(CH2)2-R 1 ,S-(CH2)2-SO2-(CH2)2-S-(CH2)2-SO2-(CH2)2-R 1, S-(CH2)2-SO2-(CH2)2-SO2-(CH2)2-SO2-(CH2)2-R 1 , S-(CH2)2-O-(CH2)2-SO2-(CH2)2-O-(CH2)2-R 1 , S-(CH2)3-(CF2)-(CH2)3-R 1 , S-(CH2)-(CF2)3-(CH2)-R 1 , S-(CH2)2-(CF2)4-(CH2)2-R 1 , S-(CH2)-[CH(CF3)]-(CH2)-R 1 , S-(CH2)-[C(CH3)CF3]-(CH2)-R 1 , S-(CH2)-[CH(CH2CF3)]-(CH2)-R 1 , S-(CH2)-[C(CH3)(CH2CF3)]-(CH2)-R 1 , S-(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-R 1 and S-(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-R 1 , wherein R1 is selected from the group consisting of alkenyls of formula (4-1), (4-2), (4-3), (4-4), (4-5), (4-6), (4-7), (4-8), (4-9), (4-10), (4-11) or (4-12);

[0341] SO2-(CH2)5-R 1 , SO2-(CH2)6-R 1 , SO2-(CH2)7-R 1 , SO2-(CH2)8-R 1 , SO2-(CH2)9-R 1 , SO2-(CH2) 10 -R 1 , SO2-(CH2) 11 -R 1 , SO2-(CH2) 12 -R 1 , SO2-(CH2) 13 -R 1 , SO2-(CH2)2-S-(CH2)2-R 1 , SO2-(CH2)2-SO2-(CH2)2-R 1、SO2-(CH2)2-S-(CH2)2-S-(CH2)2-R 1 SO2-(CH2)2-O-(CH2)2-O-(CH2)2-R 1 SO2-(CH2)2-S-(CH2)2-O-(CH2)2-R 1 SO2-(CH2)2-SO2-(CH2)2-O-(CH2)2-R 1 SO2-(CH2)2-SO2-(CH2)2-S-(CH2)2-R 1 、SO2-(CH2)2-O-(CH2)2-O-(CH2)2-O-(CH2)2-R 1 、SO2-(CH2)2-O-(CH2)2-S-(CH2)2-O-(CH2)2-R 1 、SO2-(CH2)2-S-(CH2)2-O-(CH2)2-S-(CH2)2-R 1 SO2-(CH2)2-SO2-(CH2)2-O-(CH2)2-SO2-(CH2)2-R 1 、SO2-(CH2)2-S-(CH2)2-S-(CH2)2-S-(CH2)2-R 1 SO2-(CH2)2-SO2-(CH2)2-S-(CH2)2-SO2-(CH2)2-R 1 SO2-(CH2)2-SO2-(CH2)2-SO2-(CH2)2-SO2-(CH2)2-R 1 SO2-(CH2)2-O-(CH2)2-SO2-(CH2)2-O-(CH2)2-R 1 SO2-(CH2)3-(CF2)-(CH2)3-R 1 SO2-(CH2)-(CF2)3-(CH2)-R 1 SO2-(CH2)2-(CF2)4-(CH2)2-R 1 SO2-(CH2)-[CH(CF3)]-(CH2)-R 1 SO2-(CH2)-[C(CH3)CF3]-(CH2)-R 1 SO2-(CH2)-[CH(CH2CF3)]-(CH2)-R 1 SO2-(CH2)-[C(CH3)(CH2CF3)]-(CH2)-R 1 、SO2-(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-R1 and SO2-(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-R 1 R1 is selected from the group consisting of alkenyl groups of free formulas (4-1), (4-2), (4-3), (4-4), (4-5), (4-6), (4-7), (4-8), (4-9), (4-10), (4-11), or (4-12).

[0342] Therefore, the substituents N-R2-R1 in formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), and (I”) are particularly preferably selected from the group consisting of the following:

[0343] N-(CH2)5-R 1 N-(CH2)6-R 1 N-(CH2)7-R 1 N-(CH2)8-R 1 N-(CH2)9-R 1 N-(CH2) 10 -R 1 N-(CH2) 11 -R 1 N-(CH2) 12 -R 1 N-(CH2) 13 -R 1 N-(CH2)2-S-(CH2)2-R 1 N-(CH2)2-SO2-(CH2)2-R 1 ,N-(CH2)2-S-(CH2)2-S-(CH2)2-R 1 ,N-(CH2)2-O-(CH2)2-O-(CH2)2-R 1 ,N-(CH2)2-S-(CH2)2-O-(CH2)2-R 1 ,N-(CH2)2-SO2-(CH2)2-O-(CH2)2-R 1 , N-(CH2)2-SO2-(CH2)2-S-(CH2)2-R 1 , N-(CH2)2-O-(CH2)2-O-(CH2)2-O-(CH2)2-R 1 , N-(CH2)2-O-(CH2)2-S-(CH2)2-O-(CH2)2-R 1, N-(CH2)2-S-(CH2)2-O-(CH2)2-S-(CH2)2-R 1 , N-(CH2)2-SO2-(CH2)2-O-(CH2)2-SO2-(CH2)2-R 1 , N-(CH2)2-S-(CH2)2-S-(CH2)2-S-(CH2)2-R 1 , N-(CH2)2-SO2-(CH2)2-S-(CH2)2-SO2-(CH2)2-R 1 , N-(CH2)2-SO2-(CH2)2-SO2-(CH2)2-SO2-(CH2)2-R 1 , N-(CH2)2-O-(CH2)2-SO2-(CH2)2-O-(CH2)2-R 1 N-(CH2)3-(CF2)-(CH2)3-R 1 N-(CH2)-(CF2)3-(CH2)-R 1 N-(CH2)2-(CF2)4-(CH2)2-R 1 N-(CH2)-[CH(CF3)]-(CH2)-R 1 ,N-(CH2)-[C(CH3)CF3]-(CH2)-R 1 ,N-(CH2)-[CH(CH2CF3)]-(CH2)-R 1 ,N-(CH2)-[C(CH3)(CH2CF3)]-(CH2)-R 1 ,N-(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-R 1 and N-(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-R 1 R1 is selected from the group consisting of alkenyl groups of free formulas (4-1), (4-2), (4-3), (4-4), (4-5), (4-6), (4-7), (4-8), (4-9), (4-10), (4-11), or (4-12).

[0344] Particularly preferred, the compounds of formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), and (I”) contain a polymerizable group R1 represented by formulas (4-1), (4-2), (4-5), (4-6), (4-11), and (4-12).

[0345] Very particularly preferred, the compounds of formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), and (I”) contain a polymerizable group R1, which is a methacryloyl or acryloyl group represented by formulas (4-1) and (4-2).

[0346] Therefore, the present invention also relates to ophthalmic devices or precursor articles for manufacturing ophthalmic devices, comprising polymeric compounds of formula (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) and / or (I”) as described above or preferably as described above, wherein R1 is independently an acryloyl or methacryloyl group each time it appears.

[0347] Therefore, the present invention also relates to compounds of formula (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) and / or (I”) as described above or preferably as described above, wherein R1 is independently an acryloyl or methacryloyl group each time it appears.

[0348] Examples of compounds / monomers of formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) and / or (I”) are the following compounds (A-001) to (A-162) as shown in Table 1.

[0349] Table 1 :

[0350]

[0351]

[0352]

[0353]

[0354]

[0355]

[0356]

[0357]

[0358]

[0359]

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366] Some of the compounds in this application can be synthesized using methods well known to those skilled in the art. However, for the specific precursor materials of this application, a novel preparation method is described herein. Preferably, all synthesis is carried out under an inert atmosphere using a dry solvent.

[0367] An exemplary reaction sequence for compounds of formula (I#) is shown in Scheme 1, wherein X is O, Y0 is O, m1 is 1, A1 is N and A2, A3 and A4 are CR", and all other symbols and subscripts have the meanings described above and polymerizable group R1 is as shown in Scheme 1.

[0368] Option 1:

[0369]

[0370] The first type of reaction is the formation of cinnamic acid derivatives.

[0371] The second type of reaction is the oxidation of pyridine 1-oxides.

[0372] The third type of reaction is a base-induced ring-closing reaction.

[0373] The fourth type of reaction is the methoxyl deprotection reaction.

[0374] The fifth type of reaction is the Williamson ether synthesis reaction.

[0375] The sixth type of reaction is esterification.

[0376] A representative synthesis of compound A-001 is described in scheme 1-1. Part of the synthetic sequence was adapted to the desired chemical structure of A-001 by the method previously described by D. Wang et al., Org. Lett. 2017, 19, 984-987.

[0377] Option 1-1:

[0378]

[0379] The alternative reaction sequence of the compound of formula (I#) is shown in Scheme 2-1, where X is O, Y0 is O, m1 is O, A3 is N and A1 and A4 are CR", and all other symbols and subscripts have the meanings described above and the polymerizable group R1 is shown in Scheme 2-1.

[0380] Option 2-1:

[0381]

[0382] The first step of the synthesis described in Scheme 2-1 is unknown in the art and is therefore another embodiment of the present invention.

[0383] The second type of reaction is the methoxyl deprotection reaction.

[0384] The third type of reaction is the Williamson ether synthesis reaction.

[0385] The fourth type of reaction is esterification.

[0386] An alternative reaction sequence for the compound of formula (I#) is also shown in scheme 2-2, wherein X is O, Y0 is O, m1 is 1, A2 is N and A1, A3 and A4 are CR", and all other symbols and subscripts have the meanings described above and the polymerizable group R1 is shown in scheme 2-2.

[0387] Option 2-2:

[0388]

[0389] Similarly, the first type of reaction is the reaction according to the method of the present invention, which is described in further detail below.

[0390] The second type of reaction is the methoxyl deprotection reaction.

[0391] The third type of reaction is the Williamson ether synthesis reaction.

[0392] The fourth type of reaction is esterification.

[0393] The alternative reaction sequence of the compounds of formula (I#) is also shown in schemes 2-3, where X is O, Y0 is O, m1 is 0, A3 is N and A1 and A4 are CR", and all other symbols and subscripts have the meanings described above.

[0394] Option 2-3:

[0395]

[0396] The first type of reaction is the reaction according to the method of the present invention, as further described below.

[0397] The second type of reaction is the methoxyl deprotection reaction.

[0398] The third type of reaction is the Williamson ether synthesis reaction.

[0399] The fourth type of reaction is the hydrosilylation reaction.

[0400] Therefore, the present invention also relates to a method for preparing compounds of the formula (syn-Ia), (syn-Ib), (syn-Ic), (syn-Id), (syn-Ie), (syn-If), (syn-Ig), (syn-Ih), (syn-Ii), (syn-Ij), (syn-Ik), (syn-IL), (syn-Im), (syn-In), (syn-Io), (syn-Ip), (syn-Iq), (syn-Ir), or (syn-Is).

[0401]

[0402]

[0403]

[0404]

[0405]

[0406] Where A1, A2, A3, and A4 are each independently CR", R3 is H, and m1, Y, R2, R4, and "and R" has the meaning as described above, or preferably as described above.

[0407] The method adopts (syn-1-a), (syn-1-b), (syn-1-c), (syn-1-d), (syn-1-e), (syn-1-f), (syn-1-g), (syn-1-h), (syn-1-i), (sy Compounds of n-1-j), (syn-1-k), (syn-1-L), (syn-1-m), (syn-1-n), (syn-1-o), (syn-1-p), (syn-1-q), (syn-1-r) or (syn-1-s)

[0408]

[0409] (Where A1, A2, A3, and A4 are each independently CR”, and R3 is H, and R” is defined as described above or preferably as described above.)

[0410] Compounds of formula (syn-2)

[0411]

[0412] (where m1, Y, R2, R4 and

[0413] The reaction proceeds in the presence of a buffer system (having the meaning as described above or preferably as described above or as follows).

[0414] Suitable buffer systems include lithium methoxide with acetic anhydride, potassium carbonate with acetic anhydride, cesium carbonate with acetic anhydride, potassium tert-butoxide with acetic anhydride, triethylamine with acetic anhydride, pyridine with acetic anhydride, and potassium acetate with acetic anhydride.

[0415] The preferred buffer system is potassium acetate and acetic anhydride.

[0416] The compounds of formulas (syn-1-a), (syn-1-b), (syn-1-c), (syn-1-d), (syn-1-e), (syn-1-f), (syn-1-g), (syn-1-h), (syn-1-i), (syn-1-j), (syn-1-k), (syn-1-L), (syn-1-m), (syn-1-n), (syn-1-o), (syn-1-p), (syn-1-q), (syn-1-r), (syn-1-s), and (syn-2) are commercially available or can be obtained by known synthetic methods.

[0417] The reaction can be carried out in both open and closed devices.

[0418] Preferably, the starting material is mixed in an inert gas atmosphere with an oxygen content of up to 1000 ppm. Particularly preferred is an oxygen content of less than 500 ppm, and very particularly preferred is a maximum of 100 ppm.

[0419] Therefore, the present invention also relates to the method described above, wherein compounds of formulas (syn-1-a) to (syn-1-s) and (syn-2) are used in equimolar amounts.

[0420] Therefore, the present invention also relates to the method described above, wherein a portion of the buffer system (i.e., potassium acetate) is used in an amount of 0.17 to 1.45 equivalents relative to the starting material. Preferably, the method uses an amount of potassium acetate of 0.38 to 1.25 equivalents. More preferably, the method uses an amount of potassium acetate of 0.45 to 1.00 equivalents.

[0421] Therefore, the present invention also relates to the method described above, wherein a portion of the buffer system (i.e., acetic anhydride) is used relative to the starting material in an amount of 5.0 to 50.0 equivalents. Preferably, the method uses an amount of acetic anhydride of 10.0 to 25.0 equivalents. More preferably, the method uses an amount of acetic anhydride of 12.5 to 20.0 equivalents.

[0422] In the method according to the invention, it is also preferred to perform a purification step after the reaction of the reactants in order to separate the final product of Formula I as described above from the by-products or reaction products.

[0423] Suitable purification steps include separating volatile components by distillation or condensation, extraction with organic solvents, or a combination of these methods. Each known separation method can be used for this purpose or in combination.

[0424] Therefore, the present invention also relates to the method described above, characterized by a purification step following the reaction.

[0425] The reaction mixture obtained from the reaction is preferably cooled to room temperature, and a protic solvent such as water is added. The resulting solid is preferably further recrystallized from an organic solvent.

[0426] Suitable solvents for recrystallization are alcohols such as methanol, ethanol, propanol, ethers such as tetrahydrofuran, diethyl ether, methyl tert-butyl ether, or dimethoxyethane, or acetone. 2-Propanol is preferred.

[0427] In one embodiment of the method according to the invention as described above, the reaction is carried out in the absence of organic solvents (pure) and only in the buffer system described above.

[0428] In a preferred embodiment of the method according to the invention, as described above or as a preferred description in its embodiments, the reaction of compounds (syn-1-a), (syn-1-b), (syn-1-c), (syn-1-d), (syn-1-e), (syn-1-f), (syn-1-g), (syn-1-h), (syn-1-i), (syn-1-j), (syn-1-k), (syn-1-L), (syn-1-m), (syn-1-n), (syn-1-o), (syn-1-p), (syn-1-q), (syn-1-r), or (syn-1-s) and (syn-2) is carried out at a reaction temperature of 50°C to 160°C. The reaction is preferably carried out at 60°C to 140°C.

[0429] Another representative method according to the invention is described in the following embodiments 2-4, wherein the starting material of formula (syn-1-a) can be replaced by any material of formulas (syn-1-c) to (syn-1-s).

[0430] Option 2-4:

[0431]

[0432] The advantage of the preparation method according to the present invention is that the reaction does not require additional organic solvents, and the materials of formulas (syn-Ia), (syn-Ib), (syn-Ic), (syn-Id), (syn-Ie), (syn-If), (syn-Ig), (syn-Ih), (syn-Ii), (syn-Ij), (syn-Ik), (syn-IL), (syn-Im), (syn-In), (syn-Io), (syn-Ip), (syn-Iq), (syn-Ir), and (syn-Is) have high solubility in organic solvents, preferably in the organic solvents described above. The precursor materials of formulas (syn-Ia), (syn-Ib), (syn-Ic), (syn-Id), (syn-Ie), (syn-If), (syn-Ig), (syn-Ih), (syn-Ii), (syn-Ij), (syn-Ik), (syn-IL), (syn-Im), (syn-In), (syn-Io), (syn-Ip), (syn-Iq), (syn-Ir), and (syn-Is) can be further easily separated from the reaction mixture.

[0433] The present invention also relates to a method for synthesizing compounds of formula (I), (I'), or (I”), wherein X is O and Y0 is O, and other symbols and subscripts have the meanings described above or below, wherein in step 1, materials of formula (syn-Ia), (syn-Ib), (syn-Ic), (syn-Id), (syn-Ie), (syn-If), (syn-Ig), (syn-Ih), (syn-Ii), (syn-Ij), (syn-Ik), (syn-IL), (syn-Im), (syn-In), (syn-Io), (syn-Ip), (syn-Iq), (syn-Ir), or (syn-Is) are prepared.

[0434]

[0435]

[0436]

[0437]

[0438]

[0439] Where A1, A2, A3, and A4 are each independently CR", R3 is H, and m1, Y, R2, R4, and "and R" has the meaning as described above, or preferably as described above.

[0440] The method adopts (syn-1-a), (syn-1-b), (syn-1-c), (syn-1-d), (syn-1-e), (syn-1-f), (syn-1-g), (syn-1-h), (syn-1-i), (sy Compounds of n-1-j), (syn-1-k), (syn-1-L), (syn-1-m), (syn-1-n), (syn-1-o), (syn-1-p), (syn-1-q), (syn-1-r) or (syn-1-s)

[0441]

[0442] (Where A1, A2, A3, and A4 are each independently CR”, and R3 is H, and R” is defined as described above or preferably as described above.)

[0443] Compounds of formula (syn-2)

[0444]

[0445] (where m1, Y, R2, R4 and

[0446] The reaction (with the meaning as described above or preferably as described above) is carried out in the presence of a buffer system as described above or preferably as described above, followed by a deprotection reaction, a Williamson ether synthesis reaction or a thioether synthesis reaction, and optionally an esterification reaction or a silylation reaction.

[0447] A representative synthesis of compound A-097 is described in schemes 2-5. As mentioned above, the first step of the synthesis is an example of the method according to the invention.

[0448] Option 2-5:

[0449]

[0450] The first type of reaction is the method of the present invention as described above.

[0451] The second type of reaction is the methoxyl deprotection reaction.

[0452] The third type of reaction is the Williamson ether synthesis reaction.

[0453] The fourth type of reaction is esterification.

[0454] As described above, or preferably as described above, the compounds / monomers of formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), and (I”) contain polymerizable groups and are predetermined as monomers for oligomerization or polymerization.

[0455] Therefore, the present invention also relates to an oligomer, polymer or copolymer comprising at least one polymeric compound of formula (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) or (I”) as described above or preferably as described above.

[0456] The term "polymer" generally refers to a molecule with a high relative molecular mass whose structure essentially comprises multiple repeats of units actually or conceptually derived from molecules with a low relative molecular mass (PAC, 1996, 68, 2291). Unless otherwise specified, the term "polymer" includes homopolymers and copolymers. The term "oligopolymer" generally refers to a molecule with a medium relative molecular mass whose structure essentially comprises multiple small units actually or conceptually derived from molecules with a lower relative molecular mass (PAC, 1996, 68, 2291). In a preferred sense according to the invention, a polymer means a compound having ≥30 repeating units, and an oligomer means a compound having >1 and <30 repeating units.

[0457] In the foregoing and hereinafter, in the formulas of polymers, oligomers, compounds, or monomer units or polymers formed from compounds of formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), or (I”), an asterisk (“*”) indicates a connection to an adjacent repeating unit or terminal group in the polymer chain or oligomer chain.

[0458] Suitable terminal groups are known to those skilled in the art and depend on the polymerization method used.

[0459] The terms “repeating unit” and “monomer unit” refer to structural repeating units (CRUs), which are the smallest structural units that repeat to form regular macromolecules, regular oligomers, regular blocks, or regular chains (PAC, 1996, 68, 2291).

[0460] Unless otherwise stated, molecular weight is expressed as number average molecular weight M. n Or weight-average molecular weight M W The determination is given by gel permeation chromatography (GPC) relative to a polystyrene standard in elution solvents such as tetrahydrofuran, chloroform (TCM), chlorobenzene, or 1,2,4-trichlorobenzene. Unless otherwise specified, tetrahydrofuran is used as the solvent. The degree of polymerization (n) refers to the degree of polymerization relative to a polystyrene standard in an eluent such as tetrahydrofuran, chloroform (TCM), chlorobenzene, or 1,2,4-trichlorobenzene. n / M U The given number-mean degree of aggregation, where M U It is the molecular weight of a single repeating unit as described in J.M. Cowie, Polymers: Chemistry & Physics of Modern Materials, Blackie, Glasgow, 1991.

[0461] In polymers comprising copolymers according to the invention, the total number of repeating units n is preferably ≥30, very preferably ≥100, most preferably ≥200, and preferably up to 5000, very preferably up to 3000, most preferably up to 2000, including any combination of the aforementioned lower and upper limits of n.

[0462] The polymers of the present invention include homopolymers, statistical copolymers, random copolymers, alternating copolymers, and block copolymers, as well as combinations thereof.

[0463] Throughout the description and claims of this specification, the words “comprise” and “contain”, and variations thereof such as “comprising” and “comprises”, mean “including but not limited to” and are not intended to exclude other components.

[0464] Preferably, the polymerizable group R1 forms a regioregular, alternating, regiorandom, statistical, block, or random homopolymer or copolymer backbone or becomes part of the polymer backbone, wherein R1 has the meaning as described above or preferably as described above.

[0465] Preferably, such oligomers, polymers, or copolymers according to the invention comprise structural units M based on formula (I), (I'), or (I”). 0

[0466]

[0467] Wherein the polymerizable group R1 polymerizes and forms a regioregular, alternating, regiorandom, statistical, block or random oligomer or polymer backbone or becomes part of a copolymer backbone each time it appears, and wherein all symbols and subscripts used in formulas (I), (I') and (I”) have the meanings as described above or preferably as described above.

[0468] The present invention also relates to ophthalmic devices or precursor articles for manufacturing ophthalmic devices as described above or preferably as follows, comprising oligomers, polymers or copolymers, said oligomers, polymers or copolymers comprising structural units M based on formulas (I), (I') or (I”) as described above or preferably as described above. 0 R1 polymerizes each time it appears and forms a regioregular, alternating, regiorandom, statistical, block or random oligomer or polymer backbone or becomes part of a copolymer backbone.

[0469] Preferably, the polymeric group R1 has the formula (1-p), (2-p), (3-p), or (4-p).

[0470] In formulas (1-p) to (4-p), the asterisk "*" indicates a connection with an adjacent repeating unit in the polymer chain or oligomer chain or with a terminal group; the asterisk "**" in formulas (1-p) to (4-p) indicates a connection with the remaining part of formula (I) as described above or preferably as described above; and R5, R6, R7, X 11 'c' has the meaning as described above, or preferably as described above.

[0471] The present invention also relates to an ophthalmic device or a precursor article for manufacturing an ophthalmic device as described above or preferably as follows, wherein the polymeric group R1 has the formula (1-p), (2-p), (3-p), or (4-p) as described above.

[0472] The present invention also relates to oligomers, polymers or copolymers as described above or preferably as follows, wherein the polymeric group R1 has the formula (1-p), (2-p), (3-p) or (4-p) as described above.

[0473] Particularly preferred are oligomers, polymers, or copolymers of this invention containing the formula (M... 0 -I'-a), (M0 -I'-b), (M 0 -I'-c), (M 0 -I'-d), (M 0 -I'-e), (M 0 -I'-f), (M 0 -I'-g), (M 0 -I'-h), (M 0 -I'-i) or (M 0 -I”) structural unit M 0 ,

[0474]

[0475] Where R1, -R2-, X, Y0, Y, A1, A2, A3, A4, R3, R4, R5, R6, R7, X 11 c and

[0476] The meaning of the description given above or preferably as given above or as follows for compounds of formula (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), or (I”).

[0477] Exclude combinations where two O atoms or one O atom and one S atom are directly connected to each other, as is known to those skilled in the art of organic chemistry.

[0478] The present invention also relates to ophthalmic devices or precursor articles for manufacturing ophthalmic devices as described above or preferably as follows, wherein structural unit M 0 Having the formula (M) as described above 0 -I'-a), (M 0 -I'-b), (M 0 -I'-c), (M 0 -I'-d), (M 0 -I'-e), (M 0 -I'-f), (M 0 -I'-g), (M 0 -I'-h), (M 0 -I'-i) or (M 0 -I”), where the asterisk “*” indicates a connection to an adjacent repeating unit in the polymer chain or oligomer chain or to a terminal group each time it appears.

[0479] Preferably, such oligomers, polymers, or copolymers according to the invention comprise the structural units (M) as described above. 0 -I'-a), (M 0 -I'-b), (M 0 -I'-c), (M 0 -I'-d), (M 0 -I'-e), (M 0 -I'-f), (M 0 -I'-g), (M 0 -I'-h), (M 0 -I'-i) or (M 0 -I”), where

[0480] -R2- is selected from -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)9-, and -(CH2) 10 -、-(CH2) 11 -、-(CH2) 12 -、-(CH2) 13-, -(CH2)2-S-(CH2)2-, -(CH2)2-SO2-(CH2)2-, -(CH2)2-S-(CH2)2-S-(CH2)2-, -(CH2)2-O-(CH2)2-O-(CH2)2-, -(CH2)2-S-(CH2)2-O-(CH2)2-, -(CH2)2-SO2-(CH2)2-O-(CH2)2-, -(CH2)2-SO2-(CH2)2-S-(CH2)2-, -(CH2)2-O -(CH2)2-O-(CH2)2-O-(CH2)2-, -(CH2)2-O-(CH2)2-S-(CH2)2-O-(CH2)2-, -(CH2)2-S-(CH2)2-O-(CH2)2-S-(CH 2)2-, -(CH2)2-SO2-(CH2)2-O-(CH2)2-SO2-(CH2)2-, -(CH2)2-S-(CH2)2-S-(CH2)2-S-(CH2)2-, -(CH2)2-SO2-(C H2)2-S-(CH2)2-SO2-(CH2)2-, -(CH2)2-SO2-(CH2)2-SO2-(CH2)2-SO2-(CH2)2-, -(CH2)2-O-(CH2)2-SO2-(CH2) 2-O-(CH2)2-, -(CH2)3-(CF2)-(CH2)3-, -(CH2)-(CF2)3-(CH2)-, -(CH2)2-(CF2)4-(CH2)2-, -(CH2)-[CH(CF3)] -(CH2)-, -(CH2)-[C(CH3)CF3]-(CH2)-, -(CH2)-[CH(CH2CF3)]-(CH2)-, -(CH2)-[C(CH3)(CH2CF3)]-(CH2)-, -(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)2- and -(CH2)-(CF2)-O-(CF2)-O-(CF2)-(CH2)-, or preferably having the meanings described above;

[0481] Y represents O, S, SO2, or a bond, or preferably has the meaning described above;

[0482] R3 is H, F, a straight-chain alkyl group having 1 to 4 carbon atoms, or a straight-chain alkoxy group having 1 to 4 carbon atoms, or preferably has the meaning described above;

[0483] X 11 The terms O, S, O-SO2, SO2-O, C(=O), OC(=O), C(=O)O, S(C=O) and (C=O)S are selected, or preferably have the meanings described above;

[0484] R6 and R7 are H;

[0485] R5 is H, methyl, ethyl, or phenyl, or preferably has the meaning described above; and

[0486] c is 1, and

[0487] X, Y0, Y, A1, A2, A3, A4 and

[0488] The meaning of the description given above or preferably as given above or as follows for compounds of formula (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), or (I”).

[0489] Preferably, such oligomers, polymers, or copolymers are contained in the ophthalmic device according to the invention or in a precursor article for manufacturing the ophthalmic device.

[0490] Particularly preferably, such oligomers, polymers, or copolymers according to the invention comprise the structural units (M) as described above. 0 -I'-a), (M 0 -I'-b), (M 0 -I'-c), (M 0 -I'-d), (M 0 -I'-e), (M 0 -I'-f), (M 0 -I'-g), (M 0 -I'-h), (M 0 -I'-i) or (M 0 -I”), where

[0491] -R2- is selected from -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)9-, and -(CH2) 10 -、-(CH2) 11 -、-(CH2) 12 -、-(CH2) 13-, -(CH2)2-S-(CH2)2-, -(CH2)2-SO2-(CH2)2-, -(CH2)2-S-(CH2)2-S-(CH2)2-, -(CH2) 2-O-(CH2)2-O-(CH2)2-, -(CH2)2-O-(CH2)2-O-(CH2)2-O-(CH2)2-, -(CH2)2-O-(CH2)2 -S-(CH2)2-O-(CH2)2-, -(CH2)2-S-(CH2)2-O-(CH2)2-S-(CH2)2-, -(CH2)2-S-(CH2)2-S-(CH2)2-S-(CH2)2-, -(CH2)2-SO2-(CH2)2-S-(CH2)2-SO2-(CH2)2-, or preferably having the meaning described above;

[0492] Y represents O, S, SO2, or a bond, or preferably has the meaning described above;

[0493] R3 is H, F, a straight-chain alkyl group having 1 to 4 carbon atoms, or a straight-chain alkoxy group having 1 to 4 carbon atoms, or preferably has the meaning described above;

[0494] X 11 The terms O, S, O-SO2, SO2-O, C(=O), OC(=O), C(=O)O, S(C=O) and (C=O)S are selected, or preferably have the meanings described above;

[0495] R6 and R7 are H;

[0496] R5 is H, methyl, ethyl, or phenyl, or preferably has the meaning described above; and

[0497] c is 1.

[0498] It is located at position 3 of the photoactive chromophore in the above-mentioned formula (I#), and

[0499] X, Y0, Y, A1, A2, A3, A4 and

[0500] The meaning of the description given above or preferably as given above or as follows for compounds of formula (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), or (I”).

[0501] Particularly preferably, such oligomers, polymers, or copolymers are contained in the ophthalmic device according to the invention or in a precursor article for manufacturing the ophthalmic device.

[0502] The copolymer may be an oligomer or a polymer comprising one or more polymeric compounds of formula (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), or (I”) as described above or preferably as described above, or one or more polymeric compounds of formula (M) as described above or preferably as described above. 0 -I'-a), (M 0 -I'-b), (M 0 -I'-c), (M 0 -I'-d), (M 0 -I'-e), (M 0 -I'-f), (M 0 -I'-g), (M 0 -I'-h), (M 0 -I'-i) and / or (M 0 -I”) structural unit M 0 Alternatively, one or more structural units (M) that are the same as or different from each other can be described below. 0 -001) to (M) 0 -162) or one or more structural units M that may be the same as or different from each other. 2 The one or more structural units M 2 In chemistry, it differs from unit M. 0 Preferably, the one or more structural units M 2Derived through the polymerization of one or more monomers, said monomers being selected from the group consisting of: styrene, ethoxyethyl methacrylate (EOEMA), methyl methacrylate (MMA), methyl acrylate, n-alkyl acrylate (the n-alkyl group contains 2-20 carbon atoms), n-alkyl methacrylate (the n-alkyl group contains 2-20 carbon atoms), isoalkyl acrylate (the isoalkyl group contains 3-20 carbon atoms), isoalkyl methacrylate (the isoalkyl group contains 3-20 carbon atoms), ethoxyethoxyethyl acrylate (EEEA), 2-hydroxyethyl methacrylate (HEMA), tetrahydrofuran methacrylate (THFMA), glycidyl methacrylate (GMA), 16-hydroxyhexadecyl acrylate, 16-Hydroxyhexadecyl methacrylate, 18-Hydroxyoctadecyl acrylate, 18-Hydroxyoctadecyl methacrylate, 2-phenoxyethyl acrylate (EGPEA), heptafluorobutyl acrylate, heptafluorobutyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, pentafluoropropyl acrylate, pentafluoropropyl methacrylate, tetrafluoropropyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, bisphenol A diacrylate-1EO / phenol (BPADA), 2-[3'-2'H-benzotriazol-2'-yl)-4'-hydroxyphenyl]ethyl methacrylate (BTPEM), or ethylene glycol dimethacrylate.

[0503] Therefore, the present invention also relates to ophthalmic devices or precursor articles for manufacturing ophthalmic devices as described above or preferably as described above, comprising a polymeric compound other than at least one of formula (I), (I') or (I') or as described above or preferably as described above, of formula (M). 0 -I'-a), (M 0 -I'-b), (M 0 -I'-c), (M 0 -I'-d), (M 0 -I'-e), (M 0 -I'-f), (M 0 -I'-g), (M 0 -I'-h), (M 0 -I'-i) and / or (M 0 -I”) structural unit M 0 Or one or more of the structural units (M) described below 0 -001) to (M) 0The polymerizable monomer other than (-162) is selected from the group consisting of: styrene, ethoxyethyl methacrylate (EOEMA), methyl methacrylate (MMA), methyl acrylate, n-alkyl acrylate (the n-alkyl group contains 2-20 C atoms), n-alkyl methacrylate (the n-alkyl group contains 2-20 C atoms), isoalkyl acrylate (the isoalkyl group contains 3-20 C atoms), isoalkyl methacrylate (the isoalkyl group contains 3-20 C atoms), ethoxyethoxyethyl acrylate (EEEA), 2-hydroxyethyl methacrylate (HEMA), tetrahydrofuran methacrylate (THFMA), glycidyl methacrylate (GMA), 16-hydroxy acrylate. Hexadecyl acrylate, 16-hydroxyhexadecyl methacrylate, 18-hydroxyoctadecyl acrylate, 18-hydroxyoctadecyl methacrylate, 2-phenoxyethyl acrylate (EGPEA), heptafluorobutyl acrylate, heptafluorobutyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, pentafluoropropyl acrylate, pentafluoropropyl methacrylate, tetrafluoropropyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, bisphenol A diacrylate-1EO / phenol (BPADA), 2-[3'-2'H-benzotriazol-2'-yl)-4'-hydroxyphenyl]ethyl methacrylate (BTPEM), or ethylene glycol dimethacrylate.

[0504] Particularly preferably, the at least one additional polymeric monomer is selected from methyl methacrylate, 2-hydroxyethyl methacrylate, 2-phenoxyethyl acrylate, ethoxyethoxyethyl acrylate, 8-methylnonyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, or mixtures thereof.

[0505] Particularly preferably, such copolymers are contained in ophthalmic devices according to the invention or in precursor articles for manufacturing ophthalmic devices.

[0506] Alternatively, the oligomer or polymer according to the invention, preferably the polymer, is a homopolymer, i.e., an oligomer or polymer, preferably the polymer, comprising one or more of the formula (M) as described above or preferably as described above. 0 -I'-a), (M 0 -I'-b), (M 0 -I'-c), (M 0 -I'-d), (M 0 -I'-e), (M 0 -I'-f), (M 0 -I'-g), (M 0 -I'-h), (M0 -I'-i) or (M 0 -I”) structural unit M 0 Or as described below (M) 0 -001) to (M) 0 -162), and all structural units M in it 0 They are the same.

[0507] Exemplary homopolymers based on formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) and / or (I”) are the following compounds (P-001) to (P-162) as shown in Table 2.

[0508] Table 2 :

[0509]

[0510]

[0511]

[0512]

[0513]

[0514]

[0515]

[0516]

[0517]

[0518]

[0519]

[0520]

[0521]

[0522]

[0523]

[0524]

[0525]

[0526]

[0527] The letter 'n' indicates the degree of aggregation as described above.

[0528] Exemplary structural unit M of compounds based on formulas (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) and / or (I”). 0 Or formula (M) 0 -I'-a), (M 0 -I'-b), (M 0 -I'-c), (M 0 -I'-d), (M 0 -I'-e), (M 0 -I'-f), (M 0 -I'-g), (M 0 -I'-h), (M 0 -I'-i) or (M 0 -I”) structural unit M 0 The following compounds (M) are shown in Table 2-1. 0 -001) to (M) 0 -162).

[0529] Table 2-1 :

[0530]

[0531]

[0532]

[0533]

[0534]

[0535]

[0536]

[0537]

[0538]

[0539]

[0540]

[0541]

[0542]

[0543]

[0544]

[0545]

[0546]

[0547]

[0548] Preferably, the copolymer according to the invention as described above, or preferably as described above, comprises one or more structural units M as described above, having substituents as described above, or preferably as described above, in a molar ratio of m1. 0 and one or more structural units M with a molar ratio of m2 2 The ratio m1:m2 is at least 0.01 and at most 100.

[0549] Particularly preferably, such copolymers are contained in ophthalmic devices according to the invention or in precursor articles for manufacturing ophthalmic devices.

[0550] The oligomers, polymers, or copolymers according to the invention as described above, or preferably as described above, can be crosslinked. Particularly preferably, such polymers or copolymers are contained in ophthalmic devices or precursor articles for manufacturing ophthalmic devices according to the invention.

[0551] The oligomers or polymers of the present invention can be prepared by any suitable method. However, it is preferred that the oligomers, polymers, and copolymers of the present invention be prepared by free radical polymerization, wherein the polymerization reaction is initiated by a suitable free radical polymerization initiator. For the purposes of the present invention, there is no particular limitation on the type of free radical polymerization initiator and it can be any suitable free radical generating compound. Such compounds are well known to those skilled in the art. Suitable polymerization initiators can be selected from thermal initiators or photoinitiators, i.e., compounds that generate free radicals by exposure to heat or irradiation with light of a suitable wavelength. Examples of suitable thermal polymerization initiators can be selected from the group comprising compounds containing one or more peroxide groups (i.e., compounds containing the group –O–O–) and / or compounds containing one or more azo groups (i.e., compounds containing the group –N≡N–).

[0552] Suitable polymerization initiators containing one or more peroxide groups can be selected, for example, from the group consisting of tert-butyl (peroxy-2-ethylhexanoate), di(tert-butylcyclohexyl)peroxydicarbonate and benzoyl peroxide.

[0553] Suitable polymerization initiators containing one or more azo groups can be selected, for example, from the group consisting of 1,1'-azobis(cyclohexanenitrile) and 2,2'-azobis(cyclohexanenitrile) (AIBN).

[0554] Suitable examples of photoinitiators are dimethylaminobenzoate / camphorquinone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) or phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO).

[0555] If a photoinitiator is used as the polymerization initiator, it is preferable that the wavelength required to decompose the photoinitiator is different from the wavelength required to irradiate the compound of this application to change its optical properties.

[0556] Preferably, the free radical initiator is used in an amount of at least 0.0001 equivalents and at most 0.1 equivalents of the main monomer. Such free radical initiators can be thermal initiators such as azobisisobutyronitrile (AIBN) or photochemical initiators such as dimethylaminobenzoate / camphorquinone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) or phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO).

[0557] The present invention also relates to a composition for polymerization.

[0558] Depending on the intended use, such compositions as described above, or preferably as described above, may contain additional different components. These additional components may, for example, be selected from the group consisting of UV absorbers, antioxidants, and crosslinking agents.

[0559] Cross-linker can also be called crosslinking agent.

[0560] The present invention also relates to a composition for polymerization comprising at least one compound of formula (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) or (I”) as described or preferably as described above, or compounds (A-001) to (A-162) as described or preferably as described above, and / or as described or preferably as described above. The description includes, but leaves at least one reactive group for polymerization, an oligomer or polymer and / or a crosslinking agent and / or a UV absorber and / or a free radical initiator, and alternative monomers that are optionally different from compounds of formula (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) or (I”) or compounds of (A-001) to (A-162).

[0561] Compositions comprising at least one compound or compound (A-001) to (A-162) of formula (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) or (I”) as described above or preferably as described above, and oligomers or polymers according to the invention as described above, are primarily used for the synthesis of block copolymers, provided that the oligomers or polymers retain at least one reactive group that can react with monomers.

[0562] The composition may include, contain, substantially consist of, or consist of the essential or optional components. All compounds or components that can be used in the composition are known and commercially available, or can be synthesized by known methods or as described herein.

[0563] The components of the composition according to the invention are in combinations such that at least 2% to 100% by weight, preferably 3% to 70% by weight, particularly preferably 4% to 51% by weight, and very particularly preferably 5% to 45% by weight, of photoactive chromophores of the polymeric formula (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), or (I”) are contained in the resulting oligomer, polymer, or copolymer according to the invention.

[0564] The components of the composition according to the invention are in a combination of amounts such that at least 2% to 100% by weight, preferably 3% to 70% by weight, particularly preferably 4% to 51% by weight, and very particularly preferably 5% to 45% by weight of photoactive chromophores of the polymeric formula (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i), or (I”) are contained in the resulting oligomer, polymer, or copolymer according to the invention, which constitutes a material for an ophthalmic device or a precursor article for manufacturing an ophthalmic device.

[0565] There are no particular limitations on the UV absorbers that can be used in the compositions of the present invention, and they can be readily selected from those commonly known to those skilled in the art. Generally suitable UV absorbers are characterized by being unsaturated compounds, preferably compounds comprising one or more groups selected from the group consisting of olefinic groups, aryl groups, and heteroaryl groups; these groups may be present in any combination.

[0566] Suitable UV absorbers for use in the compositions of the present invention may be selected, for example, from those comprising groups selected from benzotriazole, benzophenone, and triazine. Suitable UV absorbers are disclosed, for example, in U.S. Patents 5,290,892, 5,331,073, and 5,693,095.

[0567] Suitable UV absorbers are 2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2-benzotriazolyl)phenoxy)ethyl methacrylate, 3-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2-benzotriazolyl)phenoxy)propyl methacrylate, 3-(3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl)propyl methacrylate, 3-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)propyl methacrylate, 2-(2-hydroxy-5-vinylphenyl)-2H- Benzotriazole, allyl-2-hydroxybenzophenone, 2-allyl-6-(2H-benzotriazole-2-yl)-p-cresol, 4-methacryloyloxy-2-hydroxybenzophenone, 2-(2'-hydroxy-3'-methylallyl-5'-methylphenyl)benzotriazole, 2-hydroxy-4-methacryloyloxybenzophenone, 4-acryloylethoxy-2-hydroxybenzophenone, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl methacrylate, 2-(2'-hydroxy-5'-methacryloaminophenyl)-5-methoxybenzotriazole, 2-(2'-hydroxy-5'-methacryloaminophenyl) 5-Chlorobenzotriazole, 2-(2'-hydroxy-5'-methacryloyloxypropylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methacryloyloxypropyl-3'-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole, 2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)ethyl methacrylate, 2-[3'-tert-butyl-2'-hydroxy-5'-(3'-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropyl]phenyl]-5-chlorobenzotriazole, [3'-tert-butyl-5'-(3'-dimethylvinylsilylpropoxy)-2'-hydroxyphenyl]-5-methoxybenzotriazole, 2-(tert-butyl)-6-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-4-vinylphenol, 2-(2H-1,2,3-benzotriazol-2-yl)-4-methyl-6-(2-methylprop-2-enyl)phenol, 2-(3-acetyl)-2-aminophenoxy)ethyl methacrylate, 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate, or combinations thereof.

[0568] Preferred UV absorbers are selected from the group consisting of 2-[3'-2'H-benzotriazol-2'-yl)-4'-hydroxyphenyl]ethyl methacrylate (BTPEM), 2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2-benzotriazolyl)phenoxy)ethyl methacrylate, 3-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2-benzotriazolyl)phenoxy)propyl methacrylate, and 3-(3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl)propyl methacrylate, which can be polymerized with monomers as described above or preferably as described above.

[0569] Suitable crosslinking agents can be used to impart elastomeric properties to the compositions of the present invention and ophthalmic devices or precursor articles prepared therefrom. Generally, any suitable difunctional or trifunctional monomer can be used as a crosslinking agent. Such monomers are generally well known to those skilled in the art and are selected from the group consisting of: poly(ethylene glycol) diacrylate, poly(ethylene glycol) dimethacrylate, ethylene glycol dimethacrylate (EGDMA), ethylene glycol diacrylate, 1,3-propanediol diacrylate, 1,6-hexanediol diacrylate, 1,8-octanediol diacrylate, 1,11-undecanediol diacrylate, 1,12-dodecyl diacrylate, 1,15-pentadecandediol diacrylate. Esters, 1,16-hexadecanediol diacrylate, 1,18-octadecanediol diacrylate, 1,3-propanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,8-octanediol dimethacrylate, 1,11-undecanediol dimethacrylate, 1,12-dodecyl dimethacrylate, 1,15-pentadecande ...

[0570] Preferred crosslinking agents can be selected from the following group of compounds:

[0571]

[0572] Ethylene glycol dimethacrylate (EGDMA) is particularly preferred.

[0573] Suitable antioxidants are phenyl acrylate derivatives containing hindered phenolic moieties. Preferred antioxidants are...

[0574]

[0575] Compounds or compounds (A-001) to (A-162) of formula (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) or (I”) according to the present invention, as described above or preferably as described above, and those comprising one or more of formulas (M) as described above or preferably as described above. 0 -I'-a), (M 0 -I'-b), (M 0 -I'-c), (M 0 -I'-d), (M 0 -I'-e), (M 0 -I'-f), (M 0 -I'-g), (M 0 -I'-h), (M 0 -I'-i) or (M 0 -I”) structural unit M 0 Or one or more structural units (M) 0 -001) to (M) 0 -162) The oligomers, polymers or copolymers described above or preferably as described above are particularly suitable for use in optically active devices, such as ophthalmic devices as described above.

[0576] Compounds or compounds (A-001) to (A-162) of formula (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) or (I”) according to the present invention, as described above or preferably as described above, and those comprising one or more of formulas (M) as described above or preferably as described above. 0 -I'-a), (M 0 -I'-b), (M 0 -I'-c), (M 0 -I'-d), (M 0 -I'-e), (M 0 -I'-f), (M 0 -I'-g), (M 0 -I'-h), (M 0 -I'-i) or (M 0 -I”) structural unit M 0 Or one or more structural units (M) 0 -001) to (M) 0-162) The oligomers, polymers, or copolymers described above, or preferably as described above, are particularly sensitive to two-photon or multiphoton absorption. Therefore, ophthalmic devices and precursor articles for manufacturing ophthalmic devices are sensitive to two-photon or multiphoton absorption.

[0577] The ophthalmic device according to the invention, preferably an intraocular lens system, for use in two-photon or multi-photon irradiation, is not limited. Some examples are described below.

[0578] Therefore, the present invention also relates to a precursor article for manufacturing an ophthalmic device, wherein the precursor article is a blank convertible into an optically active ophthalmic device, the optically active ophthalmic device comprising at least one oligomer, polymer, or copolymer as described above or preferably as described above, the oligomer, polymer, or copolymer comprising one or more of the formula (M) as described above or preferably as described above. 0 -I'-a), (M 0 -I'-b), (M 0 -I'-c), (M 0 -I'-d), (M 0 -I'-e), (M 0 -I'-f), (M 0 -I'-g), (M 0 -I'-h), (M 0 -I'-i) or (M 0 -I”) structural unit M 0 Or one or more structural units (M) 0 -001) to (M) 0 -162).

[0579] Preferred ophthalmic devices are optically active ophthalmic devices. Examples of such ophthalmic devices or eye implants include lenses, artificial corneas, and corneal inlays or rings. More preferably, the ophthalmic device or eye implant is a lens article. Most preferably, such an ophthalmic device is a lens. The type of lens is not limited and may include contact lenses or intraocular lenses. Most preferably, such an ophthalmic device is an intraocular lens, which may be, for example, a posterior chamber intraocular lens or an anterior chamber intraocular lens.

[0580] The blank of the present invention can be prepared as a step in a manufacturing method for making an ophthalmic device, preferably an intraocular lens, as described above. For example, but not limited to, the manufacturing method may include the following steps: polymer synthesis, polymer sheet casting, blank cutting, optical lathe cutting, optical grinding, tactile grinding or attachment, polishing, solvent extraction, sterilization, and packaging, wherein the term polymer is used as described above or preferably as described above.

[0581] The ophthalmic device of the present invention as described above, or preferably as described above, or the precursor article for manufacturing an ophthalmic device according to the present invention, can be formed by a method comprising the following steps:

[0582] - Provides a composition comprising at least one compound or compound (A-001) to (A-162) of formula (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) or (I”) as described herein or preferably as described herein, but leaving at least one reactivity for polymerization. Oligomers or polymers of the group and additional monomers and / or crosslinking agents and / or UV absorbers and / or free radical initiators of compounds or compounds (A-001) to (A-162) of formula (I), (I#), (I'), (I'-a), (I'-b), (I'-c), (I'-d), (I'-e), (I'-f), (I'-g), (I'-h), (I'-i) or (I”) as described herein; and

[0583] - Subsequently, an ophthalmic device or precursor article of the composition is formed.

[0584] The intraocular lenses according to the invention are considered to exhibit particularly advantageous properties because they are flexible enough to be rolled up or folded, and therefore require much smaller incisions to insert into the eye. This is believed to allow for improved eye healing, particularly in terms of healing time.

[0585] The type of intraocular lens is not limited in any way. For example, it can be a pseudophakic intraocular lens or a phakic intraocular lens. The former replaces the eye's natural lens, typically replacing a removed cataract lens. The latter is used to supplement existing lenses and serve as a permanent corrective lens, implanted in the anterior or posterior chamber to correct refractive errors in the eye. For example, it may include one or more optical components and one or more tactile components, wherein the one or more optical components serve as lenses, and the one or more tactile components are attached to and hold the one or more optical components in the proper position within the eye. The intraocular lens of the present invention can be a single-piece design or a multi-piece design, depending on whether the one or more optical components and the one or more tactile components are formed from a single piece of material (single-piece design) or manufactured separately and then assembled (multi-piece design). The intraocular lens of the present invention is also designed in such a way that it allows, for example, to be rolled up or folded small enough to fit an incision in the eye, the incision being as small as possible, for example, at most 3 mm in length.

[0586] Furthermore, the intraocular lens according to the present invention allows for non-invasive adjustment of optical properties, specifically polarization or refractive power, after the lens is implanted in the eye, thereby reducing the need for postoperative visual assistance or reducing or completely avoiding subsequent surgeries.

[0587] To alter the optical properties, specifically the polarization degree or refractive power, of an ophthalmic device (e.g., an intraocular lens) according to the invention, it is exposed to irradiation having a wavelength of at least 200 nm and at most 1500 nm. The irradiation is not limited and can be based on single-photon, two-photon, or multi-photon methods.

[0588] Therefore, the present invention also relates to a method for altering the optical properties of an ophthalmic device or a precursor article for manufacturing an ophthalmic device as defined herein, or preferably as defined herein, the method comprising the following steps:

[0589] - Provide an ophthalmic device as defined herein or a precursor article for manufacturing an ophthalmic device; and

[0590] -The ophthalmic device or the precursor article is then exposed to irradiation with a wavelength of at least 200 nm and at most 1500 nm.

[0591] Preferably, the irradiation has a wavelength of at least 250 nm or 300 nm, more preferably at least 350 nm, even more preferably at least 400 nm, and even more preferably at least 450 nm, and most preferably at least 500 nm. Preferably, the irradiation has a wavelength of at most 1400 nm or 1300 nm or 1200 nm or 1100 nm or 1000 nm, more preferably at most 950 nm or 900 nm, even more preferably at most 850 nm, even more preferably at most 800 nm, and most preferably at most 750 nm.

[0592] Therefore, the present invention also relates to ophthalmic devices or precursor articles for manufacturing ophthalmic devices, which can be obtained by the irradiation method described above or preferably as described above or as follows.

[0593] Alternatively, the change in refractive power can be described as a change in the refractive index of the ophthalmic device as described above or preferably as described above. Alternatively, the change in refractive power can be described as a change in the refractive index of the intraocular lens as described above or preferably as described above. The irradiation-generated refractive optical structure within the focusing volume is characterized by a change in refractive index relative to the body of the ophthalmic device or alternatively, the unirradiated portion of the ophthalmic device. The irradiation-generated refractive optical structure within the focusing volume is characterized by a change in refractive index relative to the body of the ophthalmic device or intraocular lens or alternatively, the unirradiated portion of the ophthalmic device or intraocular lens. In other words, a change in polarization or refractive index can be used to form a patterned desired refractive structure in an optical ophthalmic device as described above or preferably as described above, preferably in an intraocular lens as described above or preferably as described above.

[0594] Therefore, the present invention also relates to an ophthalmic device which can be obtained by the irradiation method described above or preferably as described above and below, having a refractive optical structure, characterized by a change in refractive index relative to the body of the ophthalmic device or alternatively the unirradiated portion of the ophthalmic device.

[0595] Preferably, a refractive structure is provided in such a manner that it exhibits a change in refractive index and shows little or no scattering loss, so that ablation or removal of the optical ophthalmic device, preferably an intraocular lens article, is not observed in the irradiated area.

[0596] In such methods, the irradiation area of ​​the ophthalmic device described above, or preferably as described above, can take the form of a two-dimensional or three-dimensional, region- or volume-filled refractive structure, which can provide spherical, aspherical, annular, or cylindrical correction. In fact, any optical structure can be formed to generate power correction in two physical directions. Furthermore, the optical structures can be stacked vertically or written into the independent planes of the ophthalmic device described above, or preferably as described above, to serve as individual lens elements.

[0597] Therefore, the present invention also relates to a method for locally adjusting the polarization degree and / or refractive index of an ophthalmic device according to the invention, preferably disposed within a patient's eye, and preferably an intraocular lens. Specifically, the method relates to creating an optical profile by adjusting the polarization degree in a non-destructive manner using a two-photon or multi-photon method. The two-photon or multi-photon method allows for different optical profiles compared to a single-photon method and can be advantageously used to manufacture ophthalmic devices according to the invention that incorporate optical profiles.

[0598] The system used for the two-photon or multi-photon method advantageously allows for non-invasive postoperative adjustment of the optical properties / profile of the implanted intraocular lens (IOL) to correct visual defects such as refractive errors. Furthermore, when manufacturing the ophthalmic device according to the invention, the system advantageously allows for gentle fabrication of the ophthalmic device to specifically allow for refractive structures that, once fabrication is complete, can provide spherical, aspherical, toroidal, or cylindrical corrections and / or maintain the flexibility of the ophthalmic device. The polarization degree of the ophthalmic device is modified based on a two-photon (or generally multi-photon) method, which allows for adjustment of the optical properties / profile of the ophthalmic device, or allows for adjustment of the optical properties in different planes of the ophthalmic device. Moreover, the modification of the polarization degree based on the two-photon or multi-photon method allows for improved maintenance of the flexibility of the ophthalmic device when processed with wavelengths from 400 nm to 590 nm.

[0599] Therefore, the present invention also relates to a method for adjusting the polarization degree of an ophthalmic device according to the present invention based on a two-photon or multi-photon absorption method, the method comprising the following steps:

[0600] Provide the ophthalmic device as described above or preferably as described above; and

[0601] The polarization degree of the ophthalmic device is adjusted by irradiating the device with the system.

[0602] The system includes:

[0603] One or more irradiation sources are used to irradiate the ophthalmic device with a two-photon or multi-photon irradiation beam, the irradiation beam being focused by an optical device and having a first wavelength and / or a second wavelength different from the first wavelength.

[0604] A scanner, coupled to the one or more irradiation sources and configured to scan the irradiation beam on the ophthalmic device, and

[0605] An input unit, coupled to the one or more irradiation sources and a scanner, is configured to input data for processing the ophthalmic device by scanning the irradiation beam on the ophthalmic device based on the input data.

[0606] The first wavelength is between 600 nm and 800 nm to locally reduce the polarization of the ophthalmic device based on the treatment, and the second wavelength is between 400 nm and 590 nm to locally increase the polarization of the ophthalmic device based on the treatment and thereby change the polymer optical material of the ophthalmic device, preferably having a significant difference in the UV / Vis spectrum relative to the unirradiated polymer optical material of the ophthalmic device.

[0607] Ultraviolet-visible spectroscopy or ultraviolet-visible spectrophotometry (UV-Vis or UV / Vis) is known to those skilled in the art. It refers to the absorption or reflectance spectrum of a portion of the ultraviolet spectral region and the entire adjacent visible spectral region. Suitable UV / Vis spectrometers are commercially available. The choice of UV / Vis spectrometer is not critical for comparing the UV / Vis spectrum of an initial ophthalmic device with the UV / Vis spectrum of the irradiated ophthalmic device prepared according to the present invention. The results can be compared as long as both measurements are performed under comparable conditions, as is known to those skilled in the art. A suitable spectrometer is the Lambda 900 UV / Vis spectrometer from PerkinElmer.

[0608] Therefore, the degree of polarization can be changed locally with exceptional precision.

[0609] The present invention also relates to a method for correcting the vision of a patient by changing the refractive index of an intraocular lens within the patient's eye, the method comprising:

[0610] Identify and measure the degree of visual correction in patients;

[0611] Determine the location and type of the refractive structure to be incorporated into the intraocular lens to correct the patient's vision; and

[0612] The intraocular lens is then exposed to two-photon or multi-photon irradiation with wavelengths between 600 nm and 800 nm to locally reduce the polarization of the intraocular lens, or to expose the intraocular lens, or

[0613] The intraocular lens is then exposed to two-photon or multi-photon irradiation with wavelengths between 400 nm and 590 nm to locally increase the polarization of the intraocular lens.

[0614] In this application, the input data is all types of data used to create a processing plan, which is defined as translating ophthalmic needs into control commands for the writing process of the ophthalmic device according to the invention. During the writing process, an optical pattern is written into the ophthalmic device by irradiation.

[0615] The term "control command" refers to a command that directly controls the writing process as defined above. Control commands can control, for example, the movement of a scanner.

[0616] The term "scanner" as used in this specification is not part of the input unit according to the invention. As used herein, "scanner" refers to a component of a system used in adjusting the polarization of the ophthalmic device according to the invention, which controls the movement of the irradiated beam.

[0617] Ophthalmic requirements refer to the desired optical profile that must be created in an ophthalmic device through the system described.

[0618] Optical profile is a desired variation defined by a surgeon based on the patient's examination results before or after implantation of an ophthalmic device, preferably an intraocular lens; such as, but not limited to, spherical total refractive power variation, toric profile, EDOF profile, or bifocal, trifocal, or multifocal profile. Alternatively, optical profile is the adjustment of the optical characteristics of the ophthalmic device.

[0619] Optical patterns are the necessary variations in polarization that cause changes in the refractive index in each voxel of an ophthalmic device.

[0620] As used herein, the term "optical device" as part of a system used in adjusting the polarization of an ophthalmic apparatus according to the invention includes all optical instruments necessary to control the spatial distribution of the irradiation source (focal point) on the ophthalmic apparatus. Key parameters of the focal point include the lateral focal size (or beam waist) and the focal length (or Rayleigh range). The optical device includes all elements that define the focal point along the beam path, such as beam expanders, aperture stops, shutters, and specifically focusing optics, such as microscope objectives or individual aspherical lenses.

[0621] Multiphoton excitation occurs only near the focal point and is preferably performed using ultrashort laser pulses. The average power is limited by a sample damage threshold, which is part of the input data as defined above.

[0622] System parameter selection and optimization criteria:

[0623] One ultimate goal is to induce a localized refractive index change in the IOL after implantation, as prescribed by a physician, to improve the patient's visual acuity. A key criterion for the refractive index change procedure is the total processing time required to achieve the desired result. It is generally accepted that such a procedure should not take more than a few minutes to be considered feasible. Systems capable of locally changing the refractive index of existing technologies do not include methods for obtaining the actual processing time for IOL applications.

[0624] Discussion of system trade-offs and limitations:

[0625] For a practical high-performance system capable of adjusting an ophthalmic device (generally or specifically an IOL) after implantation, it should be recognized that its sub-components must be treated as a system and therefore must be optimized together with the many interrelationships and trade-offs between the sub-components. Sub-components include the irradiation source, optics, scanner, and processing plan.

[0626] A key requirement for any system / parameter optimization is to maintain safety limits for the ophthalmic device materials during processing, or, in the case of processing an IOL, to maintain safety limits for both the materials and the eye containing its components (e.g., the retina). These requirements form the basis for the input data described above. Specifically, two main damage mechanisms from radiation from an irradiation source, preferably a pulsed laser source, can be distinguished: single-pulse damage (dielectric breakdown and avalanche breakdown) and thermal damage, where the lens material and / or the eye are subsequently heated to repeat the pulses to the same volume. For example, the average power of the pulsed irradiation source is related to heating and therefore to potential damage to the lens material and / or the eye. Therefore, when the average power of the irradiation source is kept below the overheating threshold of the lens material and / or the eye, the pulse energy and pulse repetition rate are the inverse product of the pulse energy, and the number of pulses per second (= the reciprocal of the repetition rate) equals the average power.

[0627] Average power is defined as pulse energy multiplied by the number of pulses per second, and is characterized in watts (W).

[0628] Irradiance equals flux density (W / cm²) 2 ).

[0629] Radiation exposure equals flux (J / cm²) 2 ).

[0630] A general objective is to minimize the processing time for post-implantation IOL conditioning. Theoretically, increasingly higher pulse energies with more frequent pulses (i.e., higher repetition rates) can be applied; however, at average power levels above a typical 1 watt, overheating begins to occur, leading to unsafe conditions for the IOL material and retina. Therefore, to remain within safe operating limits while completing the conditioning of the entire IOL volume within minutes, a preferred radiation exposure level can be defined. The preferred radiation exposure level is ≤5 kJ / cm². 2 Especially preferred is <1kJ / cm 2 And very particularly preferably <0.3kJ / cm 2 The radiation exposure figures described herein also apply to the processes and methods according to the invention, as further described below.

[0631] In cases where the processing plan is too extensive and would exceed laser safety limits related to overheating, the process can be interrupted to allow all affected ophthalmic device materials and tissues to cool down. After cooling, the positioning system can compare the processed voxels in the ophthalmic device with the optical pattern, and processing can then continue.

[0632] The process of adjusting the optical characteristics / profile of the ophthalmic device through this system and according to the requirements described above will be performed according to the processing plan described above. According to the processing plan, profiles such as toric, spherical, multifocal, or EDOF (extended depth of focus) can be written into the ophthalmic device according to the invention. Algorithms can be used to write profiles such as toric, spherical, multifocal, or EDOF (extended depth of focus) profiles.

[0633] By combining information about the desired optical profile with the input data, the required optical patterns and control commands for the irradiation source, optics, and scanner of the system described above can be calculated. Additional input data includes, for example, lens data, the laser energy required for specific refractive index changes of each voxel of the ophthalmic device material, and additional patient data, such as the exact location and orientation of the ophthalmic device in the patient's eye as part of the processing plan data.

[0634] During the writing process, control commands can be updated and modified using process input data, such as temperature data of the patient's eye obtained by, for example, IR temperature measurement, in-process positioning data of the irradiated beam, refraction data of the ophthalmic device or eye obtained by, for example, OCT (Optical Coherence Tomography) and / or obtained from Scheimpflug images.

[0635] In another embodiment of the input data, the input data includes lens data of the ophthalmic device, preferably the intraocular lens, and / or processing plan data related to the processing plan for the ophthalmic device. For example, lens data may include data related to one or more of the ophthalmic device's polarization degree and / or refractive index as a function of the location, shape, refractive power, cylindrical and spherical surfaces, and / or various aberrations in said dimensions, of a corresponding volume or portion of the ophthalmic device. Thus, the polarization degree can increase or decrease at a specific location or volume in one or more planes of the ophthalmic device, depending on the current polarization degree (or refractive index) and the polarization degree (or refractive index) obtained through processing.

[0636] In some examples, the processing plan calculation can generate control commands that yield one or more processing plan data, including: scanning strategy control command data for scanning strategies of the first and / or second wavelength irradiation beams on the ophthalmic device (e.g., scan pattern and / or scan sequence and / or scan speed and / or scan duration of the scan pattern and / or scan duration of the scan sequence and / or pulse duration of the pulses of the first and / or second wavelength irradiation beams (e.g., nanosecond, picosecond, or femtosecond pulses) and / or irradiation beam profile of the first and / or second wavelength irradiation beams and / or radiation (photon) density and / or radiation intensity and / or radiation intensity). The process input data includes temperature data such as the current and / or predicted temperature of the ophthalmic device during the exposure, refractive index / polarization data of the ophthalmic device to be obtained based on the exposure (the refractive index / polarization to be obtained specifically relates to the mapping of the refractive index / polarization to be obtained to a specific location / coordinate of the ophthalmic device), fracture size data of the fracture size, and input data such as eye data related to the size and / or shape of the patient's eye, positioning data related to the position and / or orientation of the ophthalmic device relative to the eye, and registration data related to the identification of the patient and / or the patient's specific eye.

[0637] Preferably, the scan strategy control command data of the scan strategy is the scan pattern and / or scan speed and / or pulse duration and / or radiation intensity, as further described below.

[0638] The parameters of the irradiated beam can then be adjusted based on lens data and / or processing plan data as defined herein, so as to precisely (locally) change the polarization / refractive index of the ophthalmic device when needed.

[0639] Preferably, the parameters of the irradiation beam are adjusted according to lens data and / or processing plan data as described above or preferably as presented herein.

[0640] Those skilled in the art will understand that optimal irradiation focusing conditions are achieved when the depth of field (Rayleigh range) of the irradiated beam matches the desired thickness of the optical structure to be written into the ophthalmic device.

[0641] Those skilled in the art will understand that optimal irradiation focusing conditions are achieved when the depth of field (Rayleigh range) of the irradiated beam is matched with the local thickness of the ophthalmic device.

[0642] In another embodiment, the lens data includes data related to the radiation absorption characteristics of the ophthalmic device (e.g., absorption and / or light attenuation coefficients, which may depend on the wavelength of light), and wherein the system is configured to adjust a first wavelength and / or a second wavelength of the ophthalmic device based on a multiphoton absorption process to locally alter the degree of polarization. For example, based on the material used in the ophthalmic device, a specific wavelength or wavelength range can be input for precise local variations in the degree of polarization of the ophthalmic device.

[0643] One or more irradiation sources, as part of a system used in adjusting the polarization of an ophthalmic device according to the invention, may include one or more pulsed lasers that can be used to generate nanosecond pulses, preferably picosecond pulses, and more preferably femtosecond pulses. Preferably, a single irradiation source is used. Particularly preferably, the one or more irradiation sources include one or more pulsed lasers for generating femtosecond pulses. Particularly preferably, a single pulsed laser is used to generate femtosecond pulses that are used for irradiation of the system according to the invention or the process and method according to the invention.

[0644] In one embodiment, the one or more irradiation sources include a laser that can be tuned to emit laser beams having a first wavelength and a second wavelength, respectively. This can be particularly advantageous because a single laser can be used to (locally) increase or decrease the polarization / refractive index of an ophthalmic device or intraocular lens as needed.

[0645] Different types of pulsed lasers are suitable as irradiation sources within the system to be used in adjusting the polarization of the ophthalmic device according to the invention. MHz lasers and kHz lasers are suitable and have their particular advantages. For example, when a MHz laser system operates at lower pulse energies, the focused laser spot can be maintained in the μm range (<1 μm to several μm), and thus can be used for precise local refractive index changes in all three dimensions, for example, to produce diffraction structures. A preferred MHz irradiation source is an 80 MHz laser with a pulse energy in the range of 0.1 nJ to 10 nJ.

[0646] On the other hand, kHz lasers operate at relatively high pulse energies, typically from 0.1 μJ to 10 μJ, thus requiring larger spot sizes, such as 10 μm to 100 μm, to avoid damaging the lens material. However, a larger laser spot size implies a larger depth of field (= long Rayleigh range) that can be equal to or exceed the thickness of the ophthalmic device material. With such a long Rayleigh range, it is not possible to change the refractive index layer by layer in the IOL; instead, the refractive index is changed uniformly only along a line surrounding the focal point. Preferred kHz irradiation sources are lasers with a repetition rate of 100 kHz to 500 kHz.

[0647] The average power of the irradiation source described above, or preferably as described above, is preferably between 300mW and 600mW, and particularly preferably between 400mW and 500mW.

[0648] The irradiation source, as part of the system used in adjusting the polarization of the ophthalmic device according to the invention, preferably comprises a tunable laser providing a variable wavelength in the range of about 680 nm to 1080 nm, such as a Ti:sapphire laser (e.g., the Chameleon Ultra II from Coherent, Santa Clara, CA, USA). The system may also include an optical parametric oscillator (e.g., the frequency-doubled Chameleon CompactOPO-Vis from Coherent, Santa Clara, CA, USA).

[0649] The irradiation source, as part of a system used in adjusting the polarization of the ophthalmic device according to the invention, particularly preferably comprises a femtosecond pump laser and an optical parametric amplifier. The pump laser emits an average power of >10 watts at a repetition rate of 0.1 kHz to 700 kHz at 1030 nm with pulses of <350 fs. The radiation from the pump laser is directed to the optical parametric amplifier, wherein the pump laser output is frequency-doubled and optically mixed to obtain a final tunable output in the wavelength range of 600 nm to 800 nm. A preferred repetition rate is between 50 kHz and 600 kHz. A particularly preferred repetition rate is between 100 kHz and 500 kHz.

[0650] The irradiation source, as part of a system used in adjusting the polarization of the ophthalmic device according to the invention, particularly preferably comprises a femtosecond pumped laser with an average power of >10 watts at 1030 nm, combined with an optical parametric amplifier, which emits irradiation pulses of <350 fs at a repetition rate of 1 kHz to 700 kHz. The radiation from the pump laser is directed to an optical parametric amplifier having one or more second harmonic stages to obtain a final optical output in the wavelength range of 400 nm to 590 nm. A preferred repetition rate is between 50 kHz and 600 kHz. A particularly preferred repetition rate is between 100 kHz and 500 kHz.

[0651] The laser type described above, or preferably as described above, generates a collimated beam with a diameter of several millimeters, which is then directed to optics and a scanner. The beam quality (characterized by the beam quality factor or beam propagation factor) is ideally between 1.0 and 1.5, more ideally between 1.0 and 1.3. According to DIN EN ISO 11146, beam quality is expressed in M... 2 The dimensions are given.

[0652] The first wavelength of the irradiated beam in the system used in adjusting the polarization degree of the ophthalmic device according to the invention is between 600 nm and 800 nm, preferably between 650 nm and 750 nm, more preferably between 670 nm and 720 nm, and even more preferably between 680 nm and 710 nm, so as to (locally) reduce the polarization degree of the IOL (and thus reduce the refractive index).

[0653] The second wavelength of the irradiated beam in the system used in adjusting the polarization degree of the ophthalmic device according to the invention is between 400 nm and 590 nm, preferably between 500 nm and 580 nm, and more preferably between 530 nm and 570 nm, so as to (locally) increase the polarization degree of the IOL (and thus increase the refractive index).

[0654] Therefore, the degree of polarization can be changed locally with exceptional precision.

[0655] Optical components within a system used in a method for adjusting the polarization degree of an ophthalmic device according to the invention:

[0656] The primary function of the optics is to focus the irradiated beam emitted from the irradiation source and controlled by the scanner onto the ophthalmic device. Key considerations, as described above, include spot size and depth of focus to minimize processing time while remaining within limits imposed by laser safety requirements and material damage, as stated above as part of the common input data. The most important characteristics of the optics are given by their numerical aperture (NA), effective focal length (EFL), and the diameter of the irradiated beam at the incident aperture of the focusing optics. Furthermore, all optical elements within the system used in adjusting the polarization of the ophthalmic device according to the invention should be selected based on diffraction-limited or near-diffraction-limited characteristics to avoid substantially degrading beam quality.

[0657] Different ophthalmic needs will require different spot sizes, as the spot size determines the achievable spatial resolution. Ideally, the spot size should be between 1 μm and 100 μm, and more ideally between 50 μm and 100 μm, to minimize processing time while maintaining a low probability of material damage.

[0658] The scanner within the system used in adjusting the polarization of the ophthalmic device according to the invention:

[0659] The scanner used in the system for adjusting the polarization of the ophthalmic device according to the invention may include a Galvano scanner, a piezoelectric scanner, a rotary scanner, or an acousto-optic modulator, or it may be digital, such as a spatial light modulator, a digital micromirror device, or a stereolithography apparatus. Preferably, the scanner used as part of the system of the invention according to this specification is selected from Galvano scanners, piezoelectric scanners, rotary scanners, acousto-optic modulators, spatial light modulators, digital micromirror devices, or stereolithography apparatus. A preferred Galvano scanner is a single-pivot scanner.

[0660] Preferably, the scanner is configured to operate at a scanning speed greater than 50 mm / s. This allows for shorter processing times. Generally, the processing time should not exceed a certain number of minutes, and each processing session is preferably less than 10 minutes, more preferably less than 5 minutes, and particularly preferably less than 3 minutes.

[0661] The processing area can be defined by the volume and size of the ophthalmic device. Typically, the diameter of the optics of the ophthalmic device or intraocular lens is 5 mm to 7 mm and the thickness is usually between 0.2 mm and 2.0 mm.

[0662] Optimal radiation exposure <1 kJ / cm 2 And more ideally <0.3kJ / cm 2 To maintain low total radiation exposure and short processing time while handling the entire volume of the ophthalmic device.

[0663] Particularly preferred is the use of random scanning patterns or staggered scanning lines to disperse the irradiation energy of the irradiation beam.

[0664] Scanning can be performed in three modes. In a bottom-up scan, the laser can travel from spot to spot with a specific dwell time on each spot ("bottom-up, spot to spot"). Alternatively, in a bottom-up scan, the laser can remain on overlapping spots ("bottom-up, overlapping spots"). Alternatively, the laser can travel at a fixed speed without remaining on any spot ("flying at a constant speed").

[0665] In one embodiment of the scanning pattern, the IOL is scanned via transpupil irradiation using an irradiation source as described above or preferably as described above. During scanning, the IOL, contained within the capsular bag, is pre-inserted through an incision in the cornea using a conventional surgical procedure. In this embodiment, the entire volume of the IOL is scanned, and the scanning is performed from bottom to top (i.e., the portion of the IOL furthest from the cornea is scanned first), thus forming an optical profile to avoid unnecessary changes in the refractive index in the optical path.

[0666] As mentioned above, a key consideration when selecting a scanning procedure is minimizing local heating of the ophthalmic device and / or the patient's eye; therefore, various variables are used in the scanning procedure. Anatomical features such as rupture and pupil size, as well as optical features such as numerical aperture and laser pulse characteristics, are considered to create a laser procedure with a specific scan rate and sequence. In this example, the relationship between lens coordinates and the eye coordinate system is automatically considered.

[0667] The parameters of the scanning procedure and / or processing plan are preferably the first and second wavelengths, scanning speed and sequence, lens positioning relative to the eye (e.g., in Cartesian coordinates), scanning strategy, the refractive index change to be obtained (optical pattern), numerical aperture of the objective lens, break, pupil and / or optical diameter of the lens (approximately 6 mm in some examples), pulse duration of the laser beam (shape, intensity, and xy positioning), laser safety when operating the laser, and alignment relative to the positioning of the lens and the eye.

[0668] In one embodiment of the system used in adjusting the polarization of the ophthalmic device according to the invention, photons generated in the laser are preferably guided by a mirror (e.g., optics 1) to, for example, a beam expander, which prepares the beam for subsequent scanning and focusing optics. After passing through the beam expander, the photons are guided to a scanner (e.g., a Galvano scanner, a piezoelectric scanner, a rotating scanner, an acousto-optic modulator, or digitized using a spatial light modulator, a digital micromirror device, or a stereolithography apparatus).

[0669] After passing through the scanner, the laser beam travels through another optics device, such as a beam splitter. In this embodiment, the beam splitter separates the beam into a main imaging beam for irradiating the ophthalmic device and a beam for monitoring beam characteristics and for positioning feedback. After the beam splitter, the beam is focused onto the ophthalmic device by an imaging group or focusing optics. In one embodiment, the imaging group includes microscope objectives to obtain high numerical aperture (for μm-level spatial resolution) or low NA optics to allow higher pulse energies in the μJ range.

[0670] The system described above, or preferably as described above, may further include a microscope objective coupled to the scanner for focusing the irradiated beam onto the ophthalmic device via the microscope objective, wherein the numerical aperture of the microscope objective is between 0.1 and 0.8, preferably between 0.2 and 0.5, and more preferably between 0.2 and 0.4. Providing a microscope objective with such a numerical aperture allows for high irradiated beam quality, particularly in terms of the focusing and resolution characteristics of beams used to process intraocular lenses.

[0671] Microscope objectives include typical lens configurations that allow for, for example, chromatic aberration correction. Microscope objectives are preferably connected to an eye interface system, typically a suction system that holds the patient's eye in a fixed position, as further described below.

[0672] In another embodiment of the objective lens used within the system described above, the objective lens is an Olympus LUCPLFLN objective lens, used to focus the irradiated beam onto the ophthalmic device.

[0673] The alternative focusing optics / imaging group is equipped with a single aspherical lens, the effective focal length of which is preferably in the range of 50 mm to 150 mm, and the numerical aperture is preferably in the range of 0.025 to 0.1.

[0674] The system described above, or preferably as described above, may further include a positioning system for determining the location of the focal point of the irradiated beam within the patient's eye, wherein the positioning system is coupled to a scanner, and wherein the irradiated beam is scanned by the scanner on the intraocular lens based on the location of the focal point of the irradiated beam within the eye.

[0675] The positioning system may include a location determination system, such as an optical coherence tomography system, a confocal microscope, or a Scheimpflug camera. The positioning system may be directly or indirectly coupled to the scanner. In some examples where a confocal microscope is used, the confocal microscope may be directly coupled to the scanner.

[0676] The location determination system described above is used to provide the positioning system with morphological feature data of the eye in order to determine the location of the laser focus based on the eye and the intraocular lens.

[0677] For confocal microscopy, a partially transparent mirror is used to allow for video imaging.

[0678] The system described above, or preferably as described above, is preferably further configured to determine the position and / or orientation of the intraocular lens relative to the eye and the exit of the irradiation beam, wherein the irradiation beam is scanned on the intraocular lens by a scanner based on the position and / or orientation of the intraocular lens relative to the eye. This can be particularly advantageous because the position of the intraocular lens may not be centered relative to the eye, and this misalignment can be taken into account when the intraocular lens is treated with the irradiation beam.

[0679] Regarding the location of the IOL, at least two coordinate systems can be considered related: the coordinate system of the eye and the coordinate system of the lens inside the eye, since the two may not be centered relative to each other.

[0680] Regarding the location of the IOL, at least two coordinate systems can be considered related: the x, y, z coordinates of the eye and the x, y, z coordinates of the lens inside the eye, since the two may not be centered relative to each other.

[0681] In one implementation, the location determination system creates input data. This input data includes, for example, data regarding the position and / or orientation of the ophthalmic device within the eye and relative to the laser beam exit, and / or the optical power mapping of the eye and / or the ophthalmic device. This data is used to calculate the optical pattern or the continuation of the processing.

[0682] Additionally, the positioning system can create input data during the writing process. This in-process input data includes, for example, data regarding the position and / or orientation of the lens of the ophthalmic device within the eye and relative to the laser beam exit, and / or the optical power mapping of the eye and / or the ophthalmic device. This data is used for in-process modification of control commands used to generate optical patterns.

[0683] The system described above, or preferably as described above, may further include a temperature management unit coupled to one or both of (i) one or more irradiation sources and (ii) a scanner, wherein the temperature management unit is configured to determine a portion of the temperature of the ophthalmic device during the treatment of the ophthalmic device by the scan, based on the irradiation beam characteristics and the ophthalmic device characteristics of the ophthalmic device, and wherein the system is configured to control one or both of (i) one or more irradiation sources and (ii) a scanner based on the temperature determination. This allows for ensuring that the eye and / or ophthalmic device are not adversely affected by the treatment performed with the irradiation beam.

[0684] Additionally, the temperature management unit is preferably configured to predict the temperature during the treatment performed by the ophthalmic device, and the input data includes the predicted temperature. This allows for preventative measures to ensure that the eye and / or the ophthalmic device are not adversely affected by treatment performed with an irradiated beam.

[0685] Alternatively, the temperature management unit is an infrared camera that records the eye's temperature and correlates the measured data with common data with calibration data to calculate the actual temperature in the eye.

[0686] In another implementation, temperature control is achieved using the temperature dependence of the refractive index. In these examples, the system includes a refractive power mapping device. Based on the deviation of the measured refractive power map and the progress of writing the predicted refractive power map, the temperature of the lens can be calculated during the process.

[0687] In another implementation, temperature control is achieved using the temperature dependence of the emission spectrum. In these examples, the system includes a UV-Vis photometer. Based on the measured deviations in the emission peak wavelength and / or peak width, the temperature of the focal spot can be calculated during the process.

[0688] The system described above, or preferably as described above, may further include an eye interface system configured to hold the patient's eye in a fixed position. The eye interface system may include a suction system for fixing the patient's eye position during treatment.

[0689] Patients can connect to the system in a lying or standing position.

[0690] The system described above, or preferably as described above, may also include a wireless or wired receiver and / or transceiver for one or more of the following: (i) sending control commands to one or more irradiation sources, (ii) sending control commands to a scanner, and (iii) inputting control command data required to create an optical pattern into the scanner.

[0691] Therefore, one or more irradiation sources and / or scanners can be remotely controlled. Additionally or alternatively, data relating to one or both of lens data and processing plan data can be stored externally to the system and made available to the system as needed and when required. In some examples, it may be preferred to provide at least a wired receiver or transceiver for controlling one or more irradiation sources and / or for controlling the scanner, in order to reduce (or avoid) any delays when sending control signals to one or more irradiation sources and / or scanners.

[0692] In another example, the receiver / transceiver sends the processing plan data and lens data to a central computing unit, which calculates the optical pattern and sends it back to the receiver as input data, which then provides it to the system.

[0693] The system described above, or preferably as described above, may further include means for locally measuring the refractive power of the ophthalmic device during the processing of the ophthalmic device. Therefore, one or more of the irradiation source, scanner, and input data can be adjusted during the processing.

[0694] The system described above, or preferably as described above, may further include a refractometer for locally measuring the refractive index of the ophthalmic device during the processing of the ophthalmic device. Therefore, one or more of the irradiation source, scanner, and input data can be adjusted during the processing.

[0695] Additional components of the photon-providing system may optionally include a cover in which all devices are built, a power unit that provides sufficient energy to the system and all subsystems, and subsystems such as a suction system and / or a cooler.

[0696] In addition to the components mentioned above, a controller, firmware, graphical user interface (GUI), and processing algorithms may also be provided. Connectivity to the system can be established via Bluetooth, Wi-Fi, or other ports such as RS-232.

[0697] The present invention also relates to a method for locally adjusting the polarization of an intraocular lens according to the invention disposed in a patient's eye, wherein the processing planning data includes one or more of the following:

[0698] Scanning strategy control command data for the scanning strategy used to scan the irradiated beam on the intraocular lens (e.g., scan pattern and / or scan sequence and / or scan speed and / or scan duration of the scan pattern and / or scan duration of the scan sequence and / or pulse duration of the pulses of the first and / or second wavelengths of the irradiated beam and / or irradiated beam profile and / or radiation (photon) density and / or radiation intensity and / or radiation power and / or radiation wavelength).

[0699] Temperature data of the current and / or predicted temperature of the intraocular lens during the exposure period.

[0700] The refractive index data to be obtained based on the exposure of the intraocular lens specifically relates to the mapping of the refractive index to a specific location / coordinate of the intraocular lens.

[0701] Fracture size data.

[0702] Eye data related to the size and / or shape of the patient's eyes.

[0703] Positioning data related to the position and / or orientation of the intraocular lens relative to the eye, and

[0704] Registration data associated with the identification of the patient and / or the patient's specific eye.

[0705] The present invention also relates to a method for locally adjusting the polarization of an intraocular lens according to the invention disposed in a patient's eye, wherein exposing the intraocular lens to the irradiation beam comprises exposing a first volume of the intraocular lens before exposing a second volume of the intraocular lens, wherein the first volume is further away from the cornea of ​​the patient's eye than the second volume.

[0706] In the foregoing, the initial step of the method may be to provide the intraocular lens.

[0707] In an example where exposing the intraocular lens to the irradiation beam includes exposing a first volume and / or plane and / or location of the intraocular lens before exposing a second volume and / or plane and / or location, the first volume and / or plane and / or location is farther from the cornea of ​​the patient's eye than the second volume and / or plane and / or location. The volume and / or plane and / or location irradiated at a later time point in the irradiation sequence may be closer to the cornea than the volume and / or plane and / or location irradiated at an earlier time point. Therefore, the volume may be associated with one or more planes of the intraocular lens.

[0708] The present invention also relates to a method for correcting the vision of a patient by changing the refractive index of an intraocular lens according to the invention within the patient's eye, the method comprising:

[0709] Identify and measure the degree of visual correction in patients;

[0710] Determine the location and type of the refractive structure to be incorporated into the intraocular lens to correct the patient's vision; and

[0711] The intraocular lens is then exposed to two-photon or multi-photon irradiation with wavelengths between 600 nm and 800 nm to locally reduce the polarization of the intraocular lens, and / or

[0712] The intraocular lens is then exposed to two-photon or multi-photon irradiation with wavelengths between 400 nm and 590 nm to locally increase the polarization of the intraocular lens, preferably by using the system and / or method described above to expose the intraocular lens to the irradiation.

[0713] As mentioned above, changes in polarization lead to changes in refractive index.

[0714] It should be noted that variations of the embodiments described in this invention are covered by the scope of this invention. Unless expressly excluded, any feature disclosed in this invention may be replaced by alternative features for the same, equivalent, or similar purpose. Therefore, unless otherwise stated, any feature disclosed in this invention should be considered as an example or equivalent or similar feature of the general series.

[0715] All features of this invention can be combined with each other in any way, unless certain features and / or steps are mutually exclusive. This is especially true of the preferred features of the invention. Similarly, features in non-essential combinations can be used alone (rather than in combination).

[0716] It should also be noted that many features, especially those of the preferred embodiments of the invention, are inventive in themselves and should not be considered merely as embodiments of the invention. Independent protection may be sought for these features as supplements to or alternatives to any currently claimed invention.

[0717] The technical teachings disclosed in this invention can be extracted and combined with other examples.

[0718] Undoubtedly, those skilled in the art can conceive of many other effective alternatives. It should be understood that the invention is not limited to the described embodiments, but covers modifications that are obvious to those skilled in the art and fall within the scope of the appended claims.

[0719] Example

[0720] The following examples are intended to illustrate the advantages of the compounds of the present invention in a non-limiting manner.

[0721] Unless otherwise specified, all synthesis was performed under an inert atmosphere using dry (i.e., anhydrous) solvents. Solvents and reagents were purchased from commercial suppliers.

[0722] DCM is used to represent dichloromethane. DMF is used to represent dimethylformamide. EE or EtOAc is used to represent ethyl acetate. THF is used to represent tetrahydrofuran. RT means room temperature.

[0723] The properties of copolymers can be studied on preforms prepared by bulk polymerization of monomers. Therefore, comonomers, crosslinking agents, and initiators are commercially available. All chemicals are of the highest purity and can be used as is.

[0724] Synthesis of precursor materials :

[0725] Example 1:

[0726]

[0727] 4-Methoxyphenylacetic acid (30.000 mmol; 1.00 equivalent; 5.087 g) was suspended in acetic anhydride (302.400 mmol; 10.08 equivalent; 30.872 g; 28.585 ml). Then, pyridine-3-carboxaldehyde (30.00 mmol; 1.00 equivalent; 3.246 g; 2.847 ml) and triethylamine (30.00 mmol; 1.00 equivalent; 3.036 g; 4.181 ml) were added. The reaction mixture was heated to 120 °C overnight. Water was added at 110 °C, the mixture was stirred for half an hour, and then cooled to room temperature. Volatiles were removed under vacuum. The crude mixture was purified by column chromatography using dichloromethane / methanol as eluent. 3.3 g of (E)-2-(4-methoxy-phenyl)-3-pyridin-3-yl-acrylic acid (45% theoretical yield) as a beige solid was isolated.

[0728] 1H NMR(500MHz,DMSO-d6)δ12.78(br s,1H),8.39(dd,J=4.8,1.6Hz,1H),8.32(d,J=2.2Hz,1H),7.72(s,1H),7.35(dt,J=8.0,1.8H z, 1H), 7.23 (dd, J = 8.0, 4.8Hz, 1H), 7.09 (d, J = 8.7Hz, 2H), 6.94 (d, J = 8.8Hz, 2H), 3.78 (s, 3H).

[0729] Similarly, other derivatives are prepared in the same manner: R1 represents reactant 2, R2 represents reactant 2, and [P] represents product.

[0730]

[0731]

[0732] 1 H NMR(500MHz,DMSO-d6)δ12.65(s,1H),8.01(d,J=2.4Hz,1H),7.73(s,1H),7.44–7.34(m, 3H), 7.22–7.15 (m, 2H), 7.11 (dd, J=8.8, 2.5Hz, 1H), 6.61 (d, J=8.7Hz, 1H), 3.80 (s, 3H).

[0733] Example 2:

[0734]

[0735] (E)-2-(4-methoxy-phenyl)-3-pyridin-3-yl-acrylic acid (11.61 mmol; 1.00 equivalent; 2.964 g) was suspended in anhydrous dichloromethane (952.125 mmol; 82.0 equivalent; 60.80 mL). The suspension was then cooled in an ice bath, and m-chloroperoxybenzoic acid (13.93 mmol; 1.20 equivalent; 3.123 g) was added. The reaction mixture was warmed to room temperature and stirred overnight. The suspension was filtered, and the collected solid was washed twice with diethyl ether and dried under vacuum. 2.83 g of (E)-2-(4-methoxy-phenyl)-3-(1-oxy-pyridin-3-yl)-acrylic acid (90% theoretical yield) was isolated as a colorless solid.

[0736] 1H NMR(500MHz,DMSO-d6)δ12.96(s,1H),8.05(d,J=7.0Hz,1H),7.92(s,1H),7.60(s,1H ),7.25(dd,J=7.9,6.6Hz,1H),7.11(d,J=8.7Hz,2H),7.02–6.85(m,3H),3.78(s,3H).

[0737] Similarly, other derivatives were prepared in the same manner:

[0738]

[0739]

[0740] 1 H NMR(500MHz,DMSO-d6)δ12.86(s,1H),7.93(d,J=2.0Hz,1H),7.63(s,1H),7.44–7.38(m, 3H), 7.21–7.19 (m, 2H), 7.04 (d, J=8.8Hz, 1H), 6.86 (dd, J=8.8, 2.1Hz, 1H), 3.90 (s, 3H).

[0741] Example 3:

[0742]

[0743] (E)-2-(4-methoxyphenyl)-3-(1-oxy-pyridin-3-yl)-acrylic acid (9.37 mmol; 1.00 equivalent; 2.54 g) was suspended in acetic anhydride (618.72 mmol; 66.00 equivalent; 63.164 g; 58.49 ml). Sodium carbonate (28.12 mmol; 3.00 equivalent; 3.89 g) and distilled water (65.62 mmol; 7.00 equivalent; 1.182 g; 1.182 ml) were then added. Gas release was visible, and the reaction mixture was stirred overnight at 130 °C. During cooling to room temperature, the reaction mixture solidified, and distilled water was added. The suspension was filtered and washed several times with more water. The solid was dried under vacuum. 2.1 g of 3-(4-methoxy-phenyl)-pyrano[2,3-b]pyridin-2-one (89% theoretical yield) as a light gray solid was isolated.

[0744] 1H NMR (500MHz, chloroform-d) δ8.51 (dd, J=4.8, 1.8Hz, 1H), 7.91 (dd, J=7.6, 1.8Hz, 1H), 7.74 (s, 1H ), 7.69 (d, J = 8.8Hz, 2H), 7.31 (dd, J = 7.5, 4.8Hz, 1H), 6.98 (d, J = 8.8Hz, 2H), 3.86 (s, 2H).

[0745] Similarly, other derivatives were prepared in the same manner:

[0746]

[0747] Example 4:

[0748]

[0749] 3-(4-methoxy-phenyl)-pyrano[2,3-b]pyridin-2-one (7.42 mmol; 1.00 equivalent; 1.88 g) was suspended in 50 mL of anhydrous dichloromethane and the solution was cooled in an ice bath. Then, boron tribromide (8.91 mmol; 1.20 equivalent; 2.23 g; 0.85 mL) dissolved in 10 mL of DCM was added dropwise. The solution was warmed overnight to room temperature, and the reaction mixture was quenched with water. The suspension was filtered, and the solid was washed several times with water. The crude solid was recrystallized using acetone and ethanol. 1.2 g of 3-(4-hydroxy-phenyl)-pyrano[2,3-b]pyridin-2-one (68% theoretical yield) as a light gray solid was isolated.

[0750] 1 H NMR(500MHz,DMSO-d6)δ9.79(s,1H),8.49(dd,J=4.8,1.9Hz,1H),8.23(dd,J=7.6,1.9Hz,1 H), 8.18 (s, 1H), 7.60 (d, J = 8.7Hz, 2H), 7.46 (dd, J = 7.6, 4.8Hz, 1H), 6.86 (d, J = 8.7Hz, 2H).

[0751] Example 5:

[0752]

[0753] 3-(4-hydroxy-phenyl)-pyran[2,3-b]pyridin-2-one (1.2 g, 5.02 mmol, 1.00 equivalent) was refluxed with potassium carbonate (2.81 g, 20.07 mmol, 4.00 equivalent) and 12-bromo-dodecano-1-ol (1.43 g, 5.27 mmol, 1.05 mmol) in acetone (40 ml) for at least 2 days. The suspension was filtered, and the solvent of the filtrate was evaporated. The crude residue was recrystallized from acetone and n-butanol to give 0.685 g of 3-[4-(12-hydroxy-dodecanooxy)-phenyl]-pyran[2,3-b]pyridin-2-one (32% theoretical yield).

[0754] 1 H NMR (500MHz, DMSO-d6) δ8.50(dd,J=4.8,1.8Hz,1H),8.24(d,J=6.1Hz,2H),7.70(d,J=8.8Hz,2H),7.48(dd,J=7.5,4.8Hz,1H),7.03(d,J=8.8Hz,2H) ,4.30(t,J=5.1Hz,1H),4.02(t,J=6.5Hz,2H),3.36(td,J=6.5,4.9Hz,2H) ,1.73(p,J=6.6Hz,2H),1.41(dt,J=12.1,5.6Hz,5H),1.34-1.22(m,17H).

[0755] Preparation of the compound according to the present invention:

[0756] Example 6.1:

[0757]

[0758] 3-[4-(12-hydroxy-dodecyloxy)-phenyl]-pyran[2,3-b]pyridin-2-one (0.67 g, 1.58 mmol, 1.00 equivalent) was dissolved in anhydrous THF (60 mL), and triethylamine (0.88 mL, 6.33 mmol, 4.00 equivalent) was added. Acryloyl chloride (0.161 mL, 1.9 mmol, 1.20 equivalent) was then added at 0 °C, and the mixture was stirred at room temperature until the reaction was complete. The reaction was quenched with 2-propanol (0.25 mL), the suspension was filtered, and the solvent in the filtrate was removed. The crude product was purified by column chromatography using CHCl3 / MeOH as the eluent. 0.375 g of 12-[4-(2-oxo-2H-pyrano[2,3-b]pyridin-3-yl)-phenoxy]-dodecyl acrylate was synthesized (49% theoretical yield).

[0759] 1H NMR (500MHz, chloroform-d) δ8.50 (dd, J=4.8, 1.8Hz, 1H), 7.91 (dd, J=7.6, 1.8Hz, 1H), 7.73 (s, 1H), 7.68 (d, J=8.8Hz,2H),7.30(dd,J=7.6,4.8Hz,1H),6.97(d,J=8.8Hz,2H),6.39(dd,J=17.3,1.4Hz,1H),6.1 2(dd,J=17.3,10.4Hz,1H),5.81(dd,J=10.4,1.4Hz,1H),4.15(t,J=6.8Hz,2H),4.01(t,J=6.6Hz,2 H), 1.80 (dt, J = 14.5, 6.6 Hz, 2H), 1.67 (p, J = 6.8 Hz, 2H), 1.46 (q, J = 7.5 Hz, 2H), 1.39-1.25 (m, 17H).

[0760] mp(DSC): 109℃

[0761] Maximum absorption (UV-Vis): 347nm

[0762] Similarly, other derivatives were prepared in the same manner:

[0763]

[0764] Compound 6a:

[0765] 1 H NMR(500MHz,DMSO-d6)δ8.61(s,1H),8.24(d,J=0.7Hz,1H),7.70–7.67(m,2H),7.48–7.4 4(m,2H),7.43–7.40(m,1H),6.83(s,1H),6.30(dd,J=17.3,1.6Hz,1H),6.16(dd,J=17.3 ,10.3Hz,1H),5.92(dd,J=10.3,1.6Hz,1H),4.34(t,J=6.6Hz,2H),4.08(t,J=6.7Hz,2H) ,1.73(p,J=6.8Hz,2H),1.59(p,J=6.7Hz,2H),1.40(p,J=6.9Hz,2H),1.35–1.21(m,16H).

[0766] mp(DSC): 88.2℃

[0767] Maximum absorption (UV-Vis): 328nm

[0768] Compound 6b:

[0769] 1 H NMR (500MHz, chloroform-d) δ7.68(s,1H),7.60–7.56(m,2H),7.48(s,1H),7.45–7.37(m,3H),6.39(dd,J=17.3,1.5Hz,1H),6.35(s,1H),6.11(dd,J=17.3, 10.4Hz,1H),5.81(dd,J=10.4,1.5Hz,1H),4.14(t,J=6.7Hz,2H),4.04–3 .97(m,2H),1.78(p,J=7.4Hz,2H),1.69–1.62(m,2H),1.38-1.24(m,17H).

[0770] mp(DSC): 87.3℃

[0771] Maximum absorption (UV-Vis): 359nm

[0772] Example 6.2:

[0773]

[0774] 3-(3,5-difluorophenyl)-7-[(11-hydroxyundecyl)oxy]-2H-pyrano[2,3-b]pyridin-2-one (0.15 g, 0.348 mmol, 1.00 equivalent) was dissolved in DCM (10 mL) and triethylamine (193 μL, 1.392 mmol, 4.00 equivalent). 4-(dimethylamino)pyridine (9 mg, 0.07 mmol, 0.20 equivalent) and methacrylic anhydride (30 μL, 0.418 mmol, 1.20 equivalent) were added at 0 °C. After stirring at room temperature for one day, methacrylic anhydride (66.2 μL, 0.189 mmol, 0.60 equivalent) was added. The reaction mixture was stirred for another day until the reaction was complete. The reaction mixture was concentrated under vacuum and subjected to column chromatography using cyclohexane / chloroform as eluent. The synthesis yielded 0.108 g of 11-{[3-(3,5-difluorophenyl)-2-oxo-2H-pyrano[2,3-b]pyridin-7-yl]oxy}undecyl 2-methylprop-2-enoate (0.21 mmol, 66% theoretical yield).

[0775] 1H NMR(500MHz,DMSO-d6)δ8.45(s,1H),8.13(d,J=8.4Hz,1H),7.54–7.48(m,2H), 7.31(tt,J=9.3,2.4Hz,1H),6.92(d,J=8.4Hz,1H),6.00(d,J=1.5Hz,1H),5.65( t,J=1.7Hz,1H),4.35(t,J=6.6Hz,2H),4.07(t,J=6.6Hz,2H),1.87(s,3H),1.75 (p,J=6.8Hz,2H),1.60(p,J=6.8Hz,2H),1.44–1.37(m,2H),1.35-1.22(m,12H).

[0776] 19 F NMR (470MHz, DMSO-d6) δ-110.0.

[0777] mp(DSC): 102℃

[0778] Maximum absorption (UV-Vis): 347nm

[0779] Synthesis of precursor materials:

[0780] Example 7:

[0781]

[0782] 2,4-Dimethoxypyridine (15.00 g; 103.48 mmol; 1.00 equivalent) was dissolved in anhydrous acetonitrile (140.53 mL; 2.69 mol; 26.00 equivalent), and N-bromosuccinimide (18.60 g; 103.48 mmol; 1.00 equivalent) was added. The reaction mixture was refluxed overnight until the reaction was complete. The solvent was removed under reduced pressure, and the crude product was purified by column chromatography using heptane / ethyl acetate as eluent. 16.65 g of 5-bromo-2,4-dimethoxypyridine (74% theoretical yield) was isolated, along with 4.42 g of 3-bromo-2,4-dimethoxypyridine (20% theoretical yield) as a byproduct.

[0783] 1 H NMR (500MHz, DMSO-d6) δ8.15(s,1H),6.53(s,1H),3.89(s,4H),3.83(s,3H).

[0784] Similarly, other derivatives were prepared in the same manner:

[0785]

[0786]

[0787] Compound 7a:

[0788] 1 ¹H NMR (500MHz, chloroform-d) δ 7.99 (dd, J = 5.7, 2.1Hz, 1H), 6.52 (dd, J = 5.8, 2.0Hz, 1H), 4.00 (d, J = 1.9Hz, 3H), 3.94 (d, J = 2.1Hz, 3H).

[0789] Compound 7c:

[0790] 1 ¹H NMR (500MHz, chloroform-d) δ 7.69 (dd, J = 2.4Hz), 6.73 (dd, J = 2.4Hz), 3.89 (s, 3H), 3.87 (s, 3H).

[0791] Compound 7d:

[0792] 1 ¹H NMR (500MHz, chloroform-d) δ 6.73 (s, 2H), 3.94 (s, 6H).

[0793] Example 8:

[0794]

[0795] Under argon atmosphere, in a Schlenk flask, a 2M n-butyllithium solution in hexane (10 mL, 20 mmol, 1.0 equivalence) was added over 1 minute via syringe to a mixture of 2M isopropyl magnesium chloride in THF (5 mL, 10 mmol, 0.5 equivalence) and anhydrous THF (52 mL), cooled (0 °C) and stirred. The mixture was stirred for 5 minutes to obtain a yellow solution, which was then cooled to -2 °C to 0 °C. A solution of 5-bromo-2,4-dimethoxypyridine (4.361 g, 20 mmol, 1.0 equivalence) in 15 mL of anhydrous THF was added via syringe, and the resulting solution was stirred at -2 °C to 0 °C for 45 minutes. Then, N,N-dimethylformamide (4.65 mL, 3.0 equivalence) was added, and the mixture was continuously stirred at 0 °C for 30 minutes, followed by stirring at room temperature for 45–60 minutes. A saturated aqueous solution of NH4Cl was added, the aqueous layer was separated, and then extracted with EtOAc. The combined organic layers were dried over MgSO4, filtered, concentrated under vacuum, and purified by recrystallization using a mixture of methanol and distilled water to give 2.57 g of 4,6-dimethoxy-pyridine-3-carboxaldehyde as a yellow crystalline solid (78% theoretical yield).

[0796] 1¹H NMR (500MHz, chloroform-d) δ 10.23 (s, 1H), 8.54 (s, 1H), 6.22 (s, 1H), 4.00 (s, 3H), 3.93 (s, 3H).

[0797] Similarly, other derivatives were prepared in the same manner:

[0798]

[0799] Compound 8b:

[0800] 1 ¹H NMR (500MHz, chloroform-d) δ 10.42 (s, 1H), 8.19 (d, J = 6.0Hz, 1H), 6.58 (d, J = 6.0Hz, 1H), 4.02 (s, 3H), 3.95 (s, 4H).

[0801] Compound 8c:

[0802] 1 ¹H NMR (500MHz, chloroform-d) δ 10.20 (s, 1H), 8.09 (d, J = 2.3Hz, 1H), 6.81 (d, J = 2.3Hz, 1H), 3.97 (s, 4H), 3.96 (s, 4H).

[0803] Example 9:

[0804]

[0805] At 0 °C, 4,6-dimethoxypyridin-3-carboxaldehyde (5.90 g; 35.30 mmol; 1.00 equivalent) was added to a solution of benzoylmethyltriphenylphosphine bromide (21.71 g; 42.35 mmol; 1.20 equivalent) and triethylamine (5.91 mL; 42.35 mmol; 1.20 equivalent) in anhydrous tetrahydrofuran (143.62 mL; 50.00 equivalent). The solution was slowly warmed to room temperature and then refluxed until complete. A saturated aqueous solution of NH4Cl was added, the aqueous layer was separated, and then extracted with EtOAc. The combined organic layers were dried over MgSO4, filtered, concentrated under vacuum, and purified by silica gel column chromatography using heptane / ethyl acetate. 7.2 g of (E)-3-(4,6-dimethoxypyridin-3-yl)-1-phenylprop-2-en-1-one (76% theoretical yield) was isolated as a red solid.

[0806] 1¹H NMR (500MHz, chloroform-d) δ 8.29 (s, 1H), 8.02–7.99 (m, 2H), 7.85 (d, J = 15.8 Hz, 1H), 7.69 (d, J = 15.8 Hz, 1H), 7.60–7.55 (m, 1H), 7.50 (dd, J = 8.2, 6.8 Hz, 2H), 6.26 (s, 1H), 3.97 (s, 3H), 3.95 (s, 3H).

[0807] Similarly, other derivatives were prepared in the same manner; R1 and R2 were the starting materials; [P] was the reaction product:

[0808]

[0809] [P] in Example 9a:

[0810] 1 ¹H NMR (500MHz, chloroform-d) δ 8.03–7.98 (m, 2H), 7.92 (d, J = 15.7 Hz, 1H), 7.79 (d, J = 8.2 Hz, 1H), 7.58–7.54 (m, 2H), 7.49 (dd, J = 8.3, 6.9 Hz, 2H), 6.37 (d, J = 8.2 Hz, 1H), 4.06 (s, 3H), 3.97 (s, 3H).

[0811] Example 10:

[0812]

[0813] (E)-3-(4,6-dimethoxypyridin-3-yl)-1-phenylprop-2-en-1-one (7.76 g; 28.82 mmol; 1.00 equivalent) was dissolved in methanol (46.75 mL; 40.00 equivalent) and tetrahydrofuran (46.69 mL; 20.00 equivalent) and cooled to 0 °C. Sodium hydroxide granules dissolved in methanol (1.15 g; 28.82 mmol; 1.00 equivalent) were added, followed by hydrogen peroxide (11.67 mL; 115.26 mmol; 4.00 equivalent; 30 wt% aqueous solution). After 0.5 hours, 0.25 mL of THF was added to dissolve the precipitate. The reaction mixture was stirred at 0 °C for 3 hours, then stirred overnight at RT. The mixture was diluted with saturated NaHCO3 and water. The aqueous phase was extracted three times with tert-butyl methyl ether. The organic phase was washed with saturated NaCl and dried over MgSO4. The crude product was purified by dissolving it in hot THF followed by the addition of heptane. The resulting precipitate was filtered and washed with heptane to give 5.13 g of 5-(3-benzoylethyleneoxy-2-yl)-2,4-dimethoxypyridine (63% theoretical yield).

[0814] 1 ¹H NMR (500MHz, chloroform-d) δ 8.07–8.03 (m, 2H), 7.99 (d, J = 0.7 Hz, 1H), 7.65–7.60 (m, 1H), 7.53–7.48 (m, 2H), 6.22 (s, 1H), 4.30 (d, J = 2.0 Hz, 1H), 4.22 (dd, J = 2.0, 0.7 Hz, 1H), 3.94 (s, 3H), 3.84 (s, 3H).

[0815] Example 11:

[0816]

[0817] 5-(3-benzoylepoxyethylene-2-yl)-2,4-dimethoxypyridine (5.13 g; 17.98 mmol; 1.00 equivalent) was placed in a flask and ethanol (52.49 mL; 50.00 equivalent) (saturated with sodium hydroxide) was added. The mixture was refluxed for 2 hours. The solvent was then removed under reduced pressure, and water was added to the residue. The aqueous phase was extracted with tert-butyl methyl ether. The aqueous phase was then acidified to pH 2 with 2 M HCl and diluted with an equal volume of saturated NaCl solution. The solution was then extracted 10 times with THF. The combined organic layers were dried over MgSO4, filtered, concentrated under vacuum, and purified by silica gel column chromatography using dichloromethane / methanol / AcOH as eluent. 3.9 g of 3-(4,6-dimethoxypyridine-3-yl)-2-hydroxy-2-phenylpropionic acid (72% theoretical yield) was isolated.

[0818] 1 H NMR(500MHz,DMSO-d6)δ12.13(br s,1H),7.90(s,1H),7.47–7.4fd5(m,2H),7.29(dd,J=8.4,6.7Hz,2H),7.25–7.22(m,1H),6.57(s,1H),5.88(br s, 1H), 3.97 (s, 3H), 3.72 (s, 3H), 3.28 (dd, J = 14.5Hz, 2H).

[0819] Example 12:

[0820]

[0821] 3-(4,6-dimethoxypyridin-3-yl)-2-hydroxy-2-phenylpropionic acid (100.00 mg; 0.33 mmol; 1.00 equivalent) was refluxed for 1 hour in a mixture of hydroiodic acid (0.92 mL; 6.97 mmol; 21.14 equivalent; 57 wt%) and acetic acid (4.56 mL; 79.79 mmol; 242.00 equivalent), and then poured onto ice. The aqueous phase was extracted four times with DCM, and the combined organic phases were dried over MgSO4. The crude product was purified by silica gel column chromatography using DCM / methanol to give 17 mg of 7-hydroxy-3-phenyl-2H-pyrano[3,2-c]pyridin-2-one (22% theoretical yield).

[0822] 1 H NMR (500MHz, DMSO-d6) δ8.13(s,1H),7.98(s,1H),7.60(dd,J=7.3,1.7Hz,2H),7.43(dd,J=8.3,6.6Hz,2H),7.40–7.36(m,1H),6.11(s,1H).

[0823] Example 13:

[0824]

[0825] 2,6-Dimethoxypyridin-3-carboxaldehyde (1.73 g; 10.35 mmol; 1.00 equivalent) was refluxed overnight at 130 °C with potassium acetate (0.772 g; 7.87 mmol; 0.76 equivalent), phenylacetic acid (1.42 g; 10.35 mmol; 1.00 equivalent), and acetic anhydride (14.26 mL; 13.5 equivalent). After cooling to room temperature, water was added and the mixture was stirred for 30 minutes. The precipitate was filtered and recrystallized from 2-propanol. 0.435 g of 7-methoxy-3-phenyl-2H-pyrano[2,3-b]pyridin-2-one was isolated (19% theoretical yield).

[0826] 1 H NMR(500MHz,DMSO-d6)δ8.27(s,1H),8.15(d,J=8.4Hz,1H),7.73–7.68(m,2H ),7.49–7.44(m,2H),7.43–7.38(m,1H),6.92(d,J=8.3Hz,1H),3.96(s,3H).

[0827] Similarly, other derivatives were prepared in the same manner; R1 and R2 were the starting materials; [P] was the reaction product:

[0828]

[0829]

[0830]

[0831]

[0832]

[0833]

[0834] 1 1H NMR (500 MHz, DMSO-d6) δ 8.54 (dd, J = 4.8, 1.8 Hz, 1H), 8.31 (s, 1H), 8.27 (dd, J = 7.6, 1.9 Hz, 1H), 7.77–7.66 (m, 2H), 7.55–7.40 (m, 4H).

[0835]

[0836] 1 1H NMR (500 MHz, chloroform-d) δ 8.41 (s, 1H), 7.79 (d, J = 0.8 Hz, 1H), 7.71–7.61 (m, 2H), 7.47–7.38 (m, 3H), 6.65 (s, 1H), 4.03 (s, 3H).

[0837]

[0838] 1 1H NMR (500 MHz, DMSO-d6) δ 8.66 (s, 1H), 8.20 (s, 1H), 7.79–7.71 (m, 2H), 7.57 (d, J = 8.7 Hz, 1H), 6.92 (s, 1H), 3.96 (s, 3H).

[0839]

[0840] 1 1H NMR (500 MHz, DMSO-d6) 8.98 (s, 1H), 8.67 (d, J = 5.7 Hz, 1H), 8.33 (s, 1H), 7.75–7.70 (m, 2H), 7.51–7.43 (m, 4H).

[0841]

[0842] 1H NMR(500MHz,DMSO-d6)δ8.13–8.10(m,1H),7.97(d,J=5.8Hz,1H),7.52(s,1H),7.19(dd,J=5.3,1.9Hz,3H),6.98–6.96(m,2H),6.63(d,J=5.9Hz,1H),3.56(s,5H),3.51(s,5H)。

[0843]

[0844] 1 H NMR(500MHz,DMSO-d6)δ8.97(s,1H),8.73(d,J=5.7Hz,1H),8.17(s,1H),7.88(dd,J=8.0,1.3Hz,1H),7.81–7.78(m,1H),7.71(tt,J=7.7,1.1Hz,1H),7.60(d,J=7.5Hz,1H),7.54(d,J=5.7Hz,1H)。

[0845]

[0846] 1 H NMR(500MHz,DMSO-d6)δ8.97(s,1H),8.66(d,J=5.7Hz,1H),8.30(s,1H),7.64(d,J=8.2Hz,2H),7.47(d,J=5.7Hz,1H),7.30(d,J=7.9Hz,2H),2.36(s,3H)。

[0847]

[0848] 1 H NMR(500MHz,DMSO-d6)δ8.67(s,1H),8.39(s,1H),7.73(d,J=8.2Hz,2H),7.40(d,J=8.0Hz,2H),6.90(s,1H),3.97(s,3H)。

[0849] 19 F NMR(470MHz,DMSO-d6)δ-60.9。

[0850]

[0851] 11H NMR (500 MHz, DMSO-d6) δ 8.41 (s, 1H), 7.95 (d, J = 8.1 Hz, 1H), 7.84 (d, J = 8.3 Hz, 1H), 7.78 (d, J = 8.0 Hz, 2H), 7.39 (d, J = 7.9 Hz, 2H), 3.95 (s, 3H).

[0852]

[0853] 1 1H NMR (500 MHz, DMSO-d6) δ 8.46 (s, 1H), 8.14 (d, J = 8.4 Hz, 1H), 7.51 (d, 2H, J = 9.0 Hz), 7.31 (tt, J = 9.3, 2.4 Hz, 1H), 6.95 (d, J = 8.4 Hz, 1H), 3.97 (s, 3H).

[0854] 19 19F NMR (470 MHz, DMSO-d6) δ -110.0.

[0855]

[0856] 1 1H NMR (500 MHz, DMSO-d6) δ 8.43 (s, 1H), 8.17 (t, J = 1.7 Hz, 1H), 8.15 (d, J = 8.4 Hz, 1H), 8.10–8.06 (m, 1H), 7.89 (dt, J = 7.8, 1.3 Hz, 1H), 7.69 (t, J = 7.9 Hz, 1H), 6.95 (d, J = 8.4 Hz, 1H), 3.97 (s, 3H).

[0857] Example 14:

[0858]

[0859] 0.446 g (1.7 mmol) of 3-[4-bromo-2-(trifluoromethoxy)phenyl]-7-methoxy-2H-pyrano[3,2-c]pyridin-2-one, 0.152 g (1.29 mmol; 1.2 equivalents) of n-pentylboronic acid, and 0.524 g (2.27 mmol; 2.1 equivalents) of tripotassium phosphate trihydrate were dissolved in 3 mL of toluene and degassed three times. 9.92 mg (0.043 mmol; 0.04 equivalents) of palladium(II) acetate and 35.92 mg (0.086 mmol; 0.08 equivalents) of 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl were then added. The reaction mixture was then stirred at 90 °C for 2 hours under a protective atmosphere. The cooled solution was diluted with 2-methyltetrahydrofuran and water, and the phases were separated. The aqueous phase was extracted three times with 2-methyltetrahydrofuran, and the organic phase was dried over MgSO4 and evaporated. The crude product was purified by silica gel column chromatography. 0.26 g of 7-methoxy-3-[4-pentyl-2-(trifluoromethoxy)phenyl]-2H-pyrano[3,2-c]pyridin-2-one was isolated (60% theoretical yield).

[0860] 1 ¹H NMR (500MHz, chloroform-d) δ 8.38 (s, 1H), 7.71 (d, J = 0.8 Hz, 1H), 7.38 (d, J = 7.7 Hz, 1H), 7.19–7.16 (m, 2H), 6.66 (s, 1H), 4.03 (s, 3H), 2.69–2.64 (m, 2H), 1.65 (dq, J = 9.6, 7.3 Hz, 2H), 1.35 (tt, J = 6.7, 2.4 Hz, 4H), 0.92–0.90 (m, 3H).

[0861] Similarly, other derivatives were prepared in the same manner; R1 and R2 were the starting materials; [P] was the reaction product:

[0862]

[0863]

[0864] Example 15:

[0865]

[0866] Anhydrous lithium chloride (0.418 g; 9.87 mmol; 5.0 equivalents) and p-toluenesulfonic acid monohydrate (1.88 g; 9.87 mmol; 5.0 equivalents) were added to a solution of 7-methoxy-3-phenyl-2H-pyrano[3,2-c]pyridin-2-one (0.5 g; 1.974 mmol) in 4 mL of anhydrous N,N-dimethylformamide. The reaction mixture was stirred at 180 °C for 2 h. Water was added at room temperature to form a precipitate, which was filtered and the filtrate was extracted three times again with DCM. The combined organic solids were dried under vacuum to give 0.376 g of 3-phenyl-2H,6H,7H-pyrano[3,2-c]pyridin-2,7-dione (80% theoretical yield).

[0867] 1 H NMR (500MHz, DMSO-d6) δ12.34(br s,1H),8.13(s,1H),7.98(s,1H),7.63–7.57(m,2H),7.46–7.41(m,2H),7.41–7.36(m,1H),6.13(s,1H).

[0868] Similarly, other derivatives were prepared in the same manner:

[0869]

[0870]

[0871] Compound 15b:

[0872] 1 H NMR (500MHz, DMSO-d6) δ12.40(s,1H),8.16(s,1H),7.85(s,1H),7.41(d,J=7.8Hz,1H),7.30(dd,J=7.9,1.6Hz,1H),7.25(d,J=2.2 Hz, 1H), 6.16 (s, 1H), 2.66 (t, J = 7.7Hz, 2H), 1.60 (p, J = 7.5Hz, 2H), 1.30 (ddq, J = 16.4, 7.3, 4.5, 2.6Hz, 4H), 0.86 (t, J = 6.9Hz, 3H).

[0873] Compound 15c:

[0874] 1H NMR (500MHz, DMSO-d6) δ12.34(br s,1H),8.40(s,1H),8.04(d,J=8.4Hz,1H),7.52–7.47(m,2H),7.29(tt,J=9.3,2.4Hz,1H),6.70(br s,1H).

[0875] Compound 15d:

[0876] 1 H NMR(500MHz,DMSO-d6)δ12.28(br s,1H),8.38(s,1H),8.15(t,J=1.7Hz,2H),8.08–8.03(m,1H),7.86(dt,J=7.7,1.4Hz,1H),7.68(t,J=7.8Hz,1H)6.71(br s,1H).

[0877] Example 16:

[0878]

[0879] 3-Phenyl-2H,6H,7H-pyrano[3,2-c]pyridine-2,7-dione (2.0 g, 8.36 mmol, 1.00 equivalent) was refluxed with potassium carbonate (4.67 g, 33.00 mmol, 4.00 equivalent) and 12-bromo-dodecane-1-ol (2.337 g, 8.79 mmol, 1.05 mmol) in N,N-dimethylformamide (35 mL) for at least 2 days. The suspension was filtered, and the solvent of the filtrate was evaporated. The crude residue was purified by column chromatography using DCM / methanol and / or heptane / ethyl acetate as eluents. 0.628 g of 7-[(12-hydroxydodecyl)oxy]-3-phenyl-2H-pyrano[3,2-c]pyridin-2-one (18% theoretical yield) and 1.95 g of 6-(12-hydroxydodecyl)-3-phenyl-2H,6H,7H-pyrano[3,2-c]pyridin-2,7-dione (55% theoretical yield) were isolated as byproducts.

[0880]

[0881] 1H NMR(500MHz,DMSO-d6)δ8.61(s,1H),8.24(s,1H),7.69(d,J=7.9Hz,2H),7.48–7.40(m,3H),6.82(s,1H),4.35 –4.30(m,3H),3.38–3.34(m,2H),1.73(p,J=6.8Hz,2H),1.39(dq,J=12.5,6.3,5.0Hz,4H),1.34–1.21(m,14H).

[0882]

[0883] 1 H NMR(500MHz,DMSO-d6)δ8.44(s,1H),7.91(s,1H),7.61–7.59(m,2H),7.46–7.43(m,2H),7.40–7.37(m,1H),6.21(s,1H),4.31(t ,J=5.1Hz,1H),3.97(t,J=7.3Hz,2H),3.38–3.34(m,2H),1.67(q,J=7.1Hz,2H),1.38(p,J=6.8Hz,2H),1.25(d,J=21.5Hz,16H).

[0884] Similarly, other derivatives were prepared in the same manner; R1 and R2 were the starting materials; [P] was the reaction product:

[0885]

[0886]

[0887] 1 H NMR (500MHz, DMSO-d6) δ8.45(s,1H),8.12(d,J=8.4Hz,1H),7.51(dd,J=9.0,2.2Hz,2H),7.31(tt,J=9.3,2.4Hz,1H),6.92(d,J=8.4Hz,1H),4. 35(t,J=6.6Hz,2H), 4.31(t,J=5.1Hz,1H), 3.36(td,J=6.6,5.2Hz,2H), 1.75(p,J=6.8Hz,2H), 1.39(p,J=7.2,6.3Hz,4H), 1.34–1.21(m,12H).

[0888]

[0889] 1H NMR(500MHz,DMSO-d6)δ7.97(s,1H),7.85–7.79(m,3H),7.72(d,J=1.7Hz,1H),7.61(t,J=7.9Hz,1H),7.53–7.49(m,1H),4.5 9–4.54(m,5H),4.48–4.43(m,2H),4.36–4.33(m,2H),4.32–4.27(m,2H),3.76(t,J=4.8Hz,2H),3.41(dt,J=10.5,5.3Hz,4H).

[0890] Example 17:

[0891] The photochemistry of polymethacrylates containing 3-phenyl-coumarin is described by characterization of melting point and comparison with reference material Ref-[1] disclosed in European Polymer Journal 51 (2014) 21-27, such as M. Schraub et al.

[0892]

[0893]

[0894] Application Examples :

[0895] Example 18 – General polymerization process for preparing bulk copolymers

[0896] To prepare the bulk polymer preform, the monomers were melted under vacuum, and their amounts and other components are shown in Table 3 below.

[0897] The compositions shown in Table 3 were formulated in the same manner as described below, mixing all compounds together while stirring. A heating bath for stirring was used if necessary. These formulations are also the basis for the copolymers compared in Table 5.

[0898] Table 3: Composition - Amounts of components are given in mol% and the corresponding amount of selected free radical initiator is added to 100 mol. you%:

[0899]

[0900]

[0901] n-BuAc = n-Butyl acrylate; EGDMA = Ethyl glycol dimethacrylate; HEMA = Hydroxyethyl methacrylate; EtMAc = Ethyl methacrylate.

[0902] a Use octadecane-1,18-dimethyldiacrylate instead of EGDMA.

[0903] b Use 8-methylnonyl acrylate instead of n-butyl acrylate.

[0904] c Using poly(ethylene glycol) diacrylate (M n 250) replaces EGDMA.

[0905] For example, a composition of 12-({2-oxo-3-phenyl-2H-pyrano[3,2-c]pyridin-7-yl}oxy)dodecylprop-2-enoate (A-097) (0.2 g, 0.42 mmol, 22.5 mol%), n-butyl acrylate (0.17 g, 1.31 mmol, 70.4 mol%), and ethylene glycol dimethacrylate (0.02 g, 0.10 mmol, 5.4 mol%) as a crosslinking agent (EGDMA) was thoroughly mixed under stirring with gentle heating and degassed by three refrigeration pump-thawing cycles. An appropriate amount (0.02 equivalent to 0.12 equivalent) of a free radical initiator (e.g., 1,1'-(3,3,5-trimethylcyclohexylene)bis[2-(1,1-dimethylethyl)-peroxide[]) was added. 231] or 2-[(E)-2-(1-cyano-1-methylethyl)diazepine-1-yl]-2-methylpropionitrile).

[0906] Two glass plates are coated with polyethylene sheets, and a 1 mm thick bubble is formed between the polyethylene sheets using a silicone rubber gasket. The coated surfaces of the glass plates are clamped together using spring clips, and a syringe needle is placed between the gasket and the polyethylene sheet. The cavity is then filled using an airtight syringe through the needle with the above-described formulation or the formulation further indicated in Table 3. Once the cavity is filled, the syringe needle is removed, the mold is sealed with a final clamp, and the assembly is placed in an oven. The polymerization temperature is between 60°C and 180°C, and individual polymerization conditions are selected for the corresponding initiator, which can be extracted from the formulation mixture by those skilled in the art. The mold is allowed to cool to room temperature before the polymer sheet is removed from the mold.

[0907] A change in refractive index was induced by irradiation in the range of 340 nm to 365 nm. The refractive index (n) of the billet at 590 nm was measured on a Schmidt+Haensch AR12 before and after irradiation. The refractive index after irradiation and the change in refractive index (maximum Δn) are shown below.

[0908] The phase transition temperature was determined using a TA Instruments Q2000 differential scanning calorimeter during a second heating operation at 20 K / min from -100 °C to 200 °C in a sealed aluminum disk.

[0909] Table 4: Results and Refractive Index Changes After Irradiation :

[0910] Example <![CDATA[T g [℃]]]> <![CDATA[n D，35℃ ]]> Δn 18-1 8.0 1.536 0.013 18-2 -5.09 1.525 0.011 18-3 9.0 1.523 0.009 18-4 -1.6 1.523 0.006 18-5 22.3 1.572 0.024 18-6 17.0 1.560 0.035 18-7 24.0 1.537 0.015 18-8 37.6 1.524 0.019

[0911] The results of Application Examples 18-5 to 18-8 show a significant change in refractive index after irradiation.

[0912] Furthermore, compared with prior art compounds, the addition of nitrogen to the photoactive chromophore according to the present invention has a significant impact on optical properties. Homopolymers of representative prior art monomers (Ref-[1], Ref-[2], Ref-[3] and Ref-[4]) and monomers A-001, A-097, A-126 and A-046 were prepared and compared to explain this effect.

[0913] Ref-[2] is the monomer (compound (M-1)) disclosed in WO2017032442.

[0914] Ref-[3] is the monomer (compound (M-42)) disclosed in WO2017032442.

[0915] Ref-[4] is the monomer (compound (M-53)) disclosed in WO2017032442.

[0916] This effect and direct comparison can be seen from the data in Table 5, and are shown below. Figure 1 middle.

[0917] Table 5: Copolymers of prior art compounds Ref-[1], Ref-[2], Ref-[3] and Ref-[4] and those obtained from Table 3 The copolymers of representative A-001, A-097, A-126, and A-046 of the formulations were compared in terms of chromophore concentration and observed refractive index. Comparison of rate changes :

[0918]

[0919]

[0920] a The percentage of photoactive chromophores per gram of total formulation (in mmol).

[0921] The photoactive chromophore ratio (in mmol) per total amount of formulation mixture (in grams) is calculated as follows: The compositions according to Table 3 consist of the various components described above. The weights in grams of all the components in each formulation are added together. Then, the amount of each photoactive chromophore in mmol (Ref-[1], Ref-[2], Ref-[3], Ref-[4], A-001, A-097, A-126, or A-046) in each formulation is divided by the sum of the previously calculated amounts of the formulations containing the respective photoactive chromophores. The quotient of this mathematical operation is the photoactive chromophore ratio (in mmol) per total amount of formulation mixture (in grams) described above.

[0922] The advantages of the compounds described in Table 5, as stated above, are shown in Table 5. Figure 1 In the figure, the refractive index change Δn is plotted relative to the amount of mmol of photoactive chromophores per gram of total formulation mixture. Figure 1 As shown, embodiments of the invention exhibit a higher refractive index change and a partially increased higher initial refractive index, and the total refractive index change per mmol of photoactive chromophore is much higher compared to the reference material used.

Claims

1. An ophthalmic device or a precursor article for the manufacture of an ophthalmic device, comprising at least one polymerized compound of formula (I) wherein the asterisk * denotes the attachment to the remainder of formula (I); X is O or S; Y0is O or S; A1, A2, A3, A4are each, independently of one another, N, CR" or C-Y-R2-R1, with the proviso that if m1is 1, only one of A1, A2, A3and A4is N and the others are CR", and with the proviso that if m1is 0, only one of A1, A2, A3and A4is N, only one of A1, A2, A3and A4is C-Y-R2-R1and the others are each, independently of one another, CR"; Y is, independently of one another, O, S, SO2or a bond; m1is 0 or 1; n1is 4; R' is, at each occurrence, independently selected from the group consisting of H, F, a linear or branched alkyl group having 1 to 20 C atoms, a linear or branched partially or completely halogenated alkyl group having 1 to 20 C atoms, a linear or branched alkoxy group having 1 to 20 C atoms, a linear or branched partially or completely halogenated alkoxy group having 1 to 20 C atoms and a linear or branched thioalkyl group having 1 to 20 C atoms, a linear or branched partially or completely halogenated thioalkyl group having 1 to 20 C atoms; R" is H; R1is a polymerizable group of formula (4) and wherein R5, R6, R7are, at each occurrence, independently of one another, selected from the group consisting of H and a linear or branched, non-fluorinated alkyl group having 1 to 20 C atoms, and c is 1; R is, at each occurrence, independently selected from the group consisting of H and a linear or branched alkyl group having 1 to 4 C atoms; o is selected from the group consisting of 0 to 20, s, t are 0 or 1, p, q are, at each occurrence, independently selected from the group consisting of 1 to 10, R0is, at each occurrence, independently selected from the group consisting of a linear or branched alkyl group having 1 to 4 C atoms; R3is H; if m1is 0, R4is R', and if m1is 1, R4is R1. ， 2. The ophthalmic device or precursor article for the manufacture of an ophthalmic device according to claim 1, wherein in the polymerized compound of formula (I), m1is 0, the compound having formula (I') wherein R1, -R2-, Y, R3, X, Y0, R', R", and R4have the meaning as described in claim 1, and wherein A1, A2, A3, A4are each, independently of one another, N, CR" or C-Y-R2-R1, with the proviso that only one of A1, A2, A3and A4is N, only one of A1, A2, A3and A4is C-Y-R2-R1and the others are each, independently of one another, CR"; and R4is R'. divalent radical of formula (B-1) ， 3. The ophthalmic device or precursor article for the manufacture of an ophthalmic device according to claim 1, wherein in the polymerized compound of formula (I), and m1is 1, the compound having formula (II) ​ ​ ​ ​ ​ ​ ​ ​ ​ ， wherein the asterisk "*" at each occurrence independently of each other denotes the attachment to the linker -R2-, -R2-Y or [Y-R2- m1 ]. ​ X 11 is selected from the group consisting of O-SO2, SO2-O, OC(=O), C(=O)O, S(C=O), and (C=O)S, ​ ​ - R2is -(C(R)2)2- o - R2is -(C(R)2)2- p - X8- (C(R)2)2- q - (X9) s - (C(R)2)2- r - (X 10 ) t - (C(R)2)2- u - ; ​ ​ X8, X9, X 10 independently at each occurrence is O, S, SO2, or NR0, ​ ​ r and u are independently selected from groups of 0 to 10 each time they appear, where –(C(R)2) p –X8–(C(R)2) q –(X9) s –(C(R)2) r –(X 10 ) t -(C(R)2) u The total number of atoms in - is at most 20. ​ ​ ​ ​ ​ ， ​ ​ ​ ​ ​ ​ ， wherein R1, -R2-, Y, R3, X, Y0, R', R" and have the meaning as described in claim 1, and A1, A2, A3, A4 are each, independently of one another, N or CR", with the proviso that only one of A1, A2, A3 and A4 is N and the others are CR".

4. The ophthalmic device or precursor article for making an ophthalmic device according to any one of claims 1 to 3, comprising an oligomer, polymer or copolymer comprising structural units M based on formula (I), (I’) or (II) 0 wherein R1 polymerizes at each occurrence, thus R1 forms a regioregular, alternating, regio- random, statistical, block or random oligomer or polymer backbone or is part of the copolymer backbone.

5. The ophthalmic device or precursor article for the manufacture of an ophthalmic device according to any one of claims 1 to 3, wherein the polymeric group R1 has the formula (4-p) ， wherein the asterisk "*" within formula (4-p) denotes the attachment to the adjacent repeating unit in the polymer chain or oligomer chain or to the terminal group, the asterisk "**" within formula (4-p) denotes the attachment to the remainder of formula (I), (I') or (I"), and R5, R6, R7, X 11 and c has the meaning according to claim 1.

6. An ophthalmic device or a precursor article for manufacturing an ophthalmic device, the ophthalmic device or a precursor article for manufacturing an ophthalmic device comprising at least one polymerized compound of the formula: (M 0 (I'-a), (M 0 (I'-b), (M 0 (I'-c), (M 0 (I'-d), (M 0 (I'-e), (M 0 (I'-f), (M 0 (I'-g), (M 0 (I'-h), (M 0 (I'-i), or (M 0 (I''). ， ， ， ， ， ， ， ， ， wherein the asterisk "*" in each occurrence denotes the attachment to the adjacent repeating unit in the polymer chain or the oligomer chain or to the terminal group; divalent radical of formula (B-1) ， The asterisk * in formula (B-1) indicates the attachment to the remainder of formula (M 0 -I'-a), (M 0 -I'-b), (M 0 -I'-c), (M 0 -I'-d), (M 0 -I'-e), (M 0 -I'-f), (M 0 -I'-g), (M 0 -I'-h), (M 0 -I'-i) or (M 0 -I''). X is O or S; Y0is O or S; A1, A2, A3, A4 in each case independently of one another in formula (M 0 A1, A2, A3, A4 in each case independently of one another in formula (M 0 A1, A2, A3, A4 in each case independently of one another in formula (M 0 A1, A2, A3, A4 in each case independently of one another in formula (M 0 A1, A2, A3, A4 in each case independently of one another in formula (M 0 A1, A2, A3, A4 in each case independently of one another in formula (M 0 A1, A2, A3, A4 in each case independently of one another in formula (M 0 A1, A2, A3, A4 in each case independently of one another in formula (M 0 A1, A2, A3, A4 in each case independently of one another in formula (M 0 A1, A2, A3, A4 in each case independently of one another in formula (M 0 A1, A2, A3, A4 in each case independently of one another in formula (M or In formula (M 0 -I'-e), (M 0 -I'-f), (M 0 -I'-g), (M 0 -I'-h) or (M 0 -I'-i), A3, A4, A1and A2are each independently of the others CR''; Y is, independently of each other, O, S, SO2 or a bond; n1is 4; R' is, at each occurrence, independently selected from the group consisting of H, F, a straight-chain or branched alkyl group having 1 to 20 C atoms, a straight-chain or branched partially or completely halogenated alkyl group having 1 to 20 C atoms, a straight-chain or branched alkoxy group having 1 to 20 C atoms, a straight-chain or branched partially or completely halogenated alkoxy group having 1 to 20 C atoms and a straight-chain or branched thioalkyl group having 1 to 20 C atoms, a straight-chain or branched partially or completely halogenated thioalkyl group having 1 to 20 C atoms; R" is H; X 11 is selected from the group consisting of O-SO2, SO2-O, OC(=O), C(=O)O, S(C=O), and (C=O)S, R5, R6, R7are, at each occurrence, independently of each other, selected from the group consisting of H and a straight-chain or branched, non-fluorinated alkyl group having 1 to 20 C atoms, c is 1 ; - R2is -(C(R)2)2- o - R2is -(C(R)2)2- p - X8- (C(R)2) q - (X9) s - (C(R)2) r - (X 10 ) t - (C(R)2) u - ; R is, at each occurrence, independently selected from the group consisting of H and a straight-chain or branched alkyl group having 1 to 4 C atoms; o is selected from the group consisting of 0 to 20, X8, X9, X 10 independently at each occurrence is O, S, SO2, or NR0, s, t are 0 or 1, p, q are, at each occurrence, independently selected from the group consisting of 1 to 10, r and u are independently selected from groups of 0 to 10 each time they appear, where –(C(R)2) p –X8–(C(R)2) q –(X9) s –(C(R)2) r –(X 10 ) t -(C(R)2) u The total number of atoms in - is at most 20. R0is, at each occurrence, independently selected from the group consisting of a straight-chain or branched alkyl group having 1 to 4 C atoms; R3is H, and R4is R'.

7. The ophthalmic device or precursor article for manufacturing an ophthalmic device according to any one of claims 1 to 3 or claim 6, wherein the ophthalmic device or precursor article for manufacturing an ophthalmic device comprises, in addition to the at least one polymerized compound of formula (I), (I'), or (I''), or formula (M) 0 -I'-a), (M 0 -I'-b), (M 0 -I'-c), (M 0 -I'-d), (M 0 -I'-e), (M 0 -I'-f), (M 0 -I'-g), (M 0 -I'-h), (M 0 -I'-i) or (M 0 -I'') structural unit M 0 In addition to at least one other polymerizable monomer, said at least one other polymerizable monomer is selected from the group consisting of: styrene, ethoxyethyl methacrylate (EOEMA), methyl methacrylate (MMA), methyl acrylate, n-alkyl acrylate having an alkyl group containing 2-20 carbon atoms, n-alkyl methacrylate having an alkyl group containing 2-20 carbon atoms, isoalkyl acrylate having an isoalkyl group containing 3-20 carbon atoms, isoalkyl methacrylate having an isoalkyl group containing 3-20 carbon atoms, ethoxyethoxyethyl acrylate (EEEA), 2-hydroxyethyl methacrylate (HEMA), tetrahydromethacrylate. Furan ester (THFMA), glycidyl methacrylate (GMA), 16-hydroxyhexadecyl acrylate, 16-hydroxyhexadecyl methacrylate, 18-hydroxyoctadecyl acrylate, 18-hydroxyoctadecyl methacrylate, 2-phenoxyethyl acrylate (EGPEA), heptafluorobutyl acrylate, heptafluorobutyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, pentafluoropropyl acrylate, pentafluoropropyl methacrylate, tetrafluoropropyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, bisphenol A diacrylate-1EO / phenol (BPADA), 2-[3'-2'H-benzotriazol-2'-yl)-4'-hydroxyphenyl]ethyl methacrylate (BTPEM), or ethylene glycol dimethacrylate.

8. The ophthalmic device or precursor article for the manufacture of an ophthalmic device according to claim 7, wherein the at least one further polymerizable monomer is selected from the group consisting of methyl methacrylate, 2-hydroxyethyl methacrylate, 2-phenoxyethyl acrylate, ethoxyethoxyethyl acrylate, 8-methylnonyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate or mixtures thereof.

9. The ophthalmic device or precursor article for making an ophthalmic device of any one of claims 1 to 3 or 6, wherein -R2- is independently for each occurrence -(C(R)2) o - and R and o have the meaning as described in claim 1.

10. The ophthalmic device or precursor article for the manufacture of an ophthalmic device according to any one of claims 1 to 3 or claim 6, wherein X is O and Y0is O.

11. The ophthalmic device or precursor article for the manufacture of an ophthalmic device according to any one of claims 1 to 3 or claim 6, wherein the polymerized R1is, at each occurrence, independently derived from an acryloyl or a methacryloyl group.

12. The ophthalmic device or precursor article for the manufacture of an ophthalmic device according to any one of claims 1 to 3 or claim 6, wherein the precursor article is a blank which can be converted into an ocular implant.

13. The ophthalmic device or precursor article for the manufacture of an ophthalmic device according to any one of claims 1 to 3 or 6, wherein the precursor article is a blank that can be transformed into an intraocular lens.

14. An ophthalmic device or precursor article for the manufacture of an ophthalmic device comprising at least one polymeric compound, wherein the compound is selected from the group consisting of: A-001； A-046； A-097; and A-126。 15. A method of forming an ophthalmic device or precursor article for the manufacture of an ophthalmic device according to any one of claims 1 to 11, the method comprising the steps of: - providing a composition comprising at least one compound of formula (I), (I’) or (I”) as defined in any one of claims 1 to 3, 9 and 10 and / or an oligomer or polymer as defined in any one of claims 4 to 8 and 11, but leaving at least one reactive group for polymerization, and optionally an additional monomer and / or crosslinker and / or UV absorber and / or free radical initiator different from the compound of formula (I), (I’) or (I”); - subsequently forming the ophthalmic device or precursor article from the composition.

16. A method of changing the optical properties of an ophthalmic device or precursor article for the manufacture of an ophthalmic device according to any one of claims 1 to 11, the method comprising the steps of: - forming an ophthalmic device or precursor article for the manufacture of an ophthalmic device according to the method of claim 15, and - subsequently exposing the ophthalmic device or the precursor article to irradiation having a wavelength of at least 200 nm and at most 1500 nm.

17. An ophthalmic device or precursor article for the manufacture of an ophthalmic device obtained by the method according to claim 16.

18. An oligomer, polymer or copolymer comprising at least one polymeric compound of formula (I) as defined in claim 1.

19. The oligomer, polymer or copolymer according to claim 18, comprising at least one further polymerizable monomer in addition to the polymerized compound of formula (I), which is selected from the group consisting of styrene, ethoxy ethyl methacrylate (EOEMA), methyl methacrylate (MMA), methyl acrylate, n-alkyl acrylates having a n-alkyl group comprising 2 to 20 C atoms, n-alkyl methacrylates having a n-alkyl group comprising 2 to 20 C atoms, iso-alkyl acrylates having an iso-alkyl group comprising 3 to 20 C atoms, iso-alkyl methacrylates having an iso-alkyl group comprising 3 to 20 C atoms, ethoxy ethoxy ethyl acrylate (EEEA), 2-hydroxyethyl methacrylate (HEMA), tetrahydrofurfuryl methacrylate (THFMA), glycidyl methacrylate (GMA), 16-hydroxyhexadecyl acrylate, 16-hydroxyhexadecyl methacrylate, 18-hydroxyoctadecyl acrylate, 18-hydroxyoctadecyl methacrylate, 2-phenoxyethyl acrylate (EGPEA), heptafluorobutyl acrylate, heptafluorobutyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, pentafluoropropyl acrylate, pentafluoropropyl methacrylate, tetrafluoropropyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, bisphenol A diacrylate-1 EO / phenol (BPADA), 2-[3'-2'H-benzotriazol-2'-yl)-4'- hydroxyphenyl]ethyl methacrylate (BTPEM) or ethylene glycol dimethacrylate.

20. Composition for polymerization, comprising at least one compound of formula (I), (I') or (I'') as claimed in any one of claims 1 to 3, 9 and 10 and / or an oligomer or polymer leaving at least one reactive group for polymerization according to claim 18 or 19, and optionally a crosslinker and / or a UV absorber and / or a free radical initiator and / or a further monomer different from the compound of formula (I), (I') or (I'').

21. A compound selected from the group consisting of: A-001； A-046； A-097; and A-126。

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