Process and device for locally polymerizing a starting material by two-color photopolymerization and method for volume printing of molded bodies

Abstract

The present invention relates to a process, an apparatus and a photoswitchable photoinitiator for locally polymerizing a starting material by bichromatic photopolymerization, as well as a method for volume printing (xolography) of shaped bodies. In particular, photoinitiators are provided that induce the curing of photopolymerizable formulations upon irradiation with two different wavelengths and can be used for volume printing (xolocure initiators).

Description

Detailed Description of the Invention

[0001] FIELD OF THE INVENTION The present invention relates to a process, an apparatus and a photoswitchable photoinitiator for locally polymerizing a starting material by bichromatic photopolymerization, as well as a method for volume printing (xolography) of molded bodies. In particular, photoinitiators are provided that induce the cure of photopolymerizable formulations upon irradiation with two different wavelengths and can be used for volume printing (xolocure initiators).

[0002] Background technology The definition of photoswitches, whose structure is photochromic, and the terminology used in this field can be found in [Bouas-Laurent, Durr, Pure and Applied Chemistry, 2001, 73, 639-665]. In general, photoswitches are photochromic compounds that can undergo a reversible structural change in at least one direction via a photochemical pathway. A typical example is the spiropyran / merocyanine system shown below:

[0003] [ka]

[0004] The colorless spiropyran is the thermodynamically favored form, which undergoes a ring-opening reaction upon irradiation with UV light to convert to a metastable colored merocyanine form (positive photochromism). The merocyanine form can be a mixture of four different isomers. Within this patent, the term merocyanine refers to one or more different E / Z isomers. The reverse reaction from merocyanine to spiropyran can be achieved either by light or heat (T-type photochromism). Spiropyran photoswitches belong to the group of chromene-based switches and are typically positive and T-type photochromic.

[0005] [ka]

[0006] In these chromene-based photoswitches, R and R' can be alkyl, alkyne, or aryl substituents, and X can be a carbon or nitrogen atom. Various derivatives of this family are photochromic, with further substitution of the aryl moiety or the oxygen atom being replaced by a nitrogen atom. The double bond in the open ring form can be in the E and / or Z configuration.

[0007] Overviews of photoinitiators, as well as terms and definitions, can be found in [Green, Industrial Photoinitiators A Technical Guide, CRC Press, 2010; Fouassier and Lalevee, Photoinitiators for Polymer Synthesis: Scope, Reactivity and Efficiency, Wiley VCH, 2012]. Curing a material refers to the polymerization of a monomer. Depending on the polymerization mechanism, several functional groups have been found to be suitable monomers. Suitable monomers include, but are not limited to, acrylates, methacrylates, thiols and enes, epoxides, oxiranes, oxetanes, or vinyl ethers. Photoinitiators initiate polymerization upon irradiation with light. Polymerization can be carried out in a radical, cationic, anionic, or metal-catalyzed manner. Photoinitiators are either Type 1, where a single compound can initiate polymerization, or Type 2, where a coinitiator is required. Type 1 photoinitiators can undergo homolytic (radical) or heterolytic bond cleavage (cationic / anionic) to form reactive species. Following reactions can generate additional species that can induce different polymerization properties. For example, an amine radical is first generated by homolytic bond cleavage, which then abstracts a hydrogen atom from the environment to form an amine, initiating base-mediated polymerization. Type 2 photoinitiators can initiate polymerization by two different mechanisms. The first mechanism is hydrogen abstraction from the co-initiator, generating two radicals that can then induce additional reactive species through subsequent reactions. The second mechanism is a photoredox reaction, in which electrons are transferred between the co-initiator and the photoinitiator. The photoredox reaction can proceed through a further proton transfer reaction to generate a radical, or other subsequent reactions that result in additional reactive species such as acids, bases, or radicals. Several structural motifs are known to initiate polymerization, and examples of the most important ones are listed below.

[0008] [ka]

[0009] Additive manufacturing, or 3D printing, can be performed using a variety of techniques and materials, allowing for the production of customized parts. Compared to injection molding, additive manufacturing allows for the creation of more complex structures, saving material and providing the opportunity to build specialized parts for machines with superior performance. However, most additive manufacturing techniques rely on a layer-by-layer build sequence. Thus, an object is sliced ​​into many layers, with one layer printed after the others. As a result, there are inherent limitations, such as the need for support structures to prevent protruding parts from falling off. Several mechanical steps are usually included between printing layers, lengthening production times. The starting material for printing must be in a form that allows for mechanical manipulation without destroying the object, which limits the starting material to a specific powder size or viscosity.

[0010] One of the most prominent 3D printing techniques is stereolithography [Hull, US 4,575,330, 1984] and related techniques. Generally, a thin layer of photocurable resin is irradiated with a specific pattern of light at one wavelength. This induces photopolymerization, resulting in hardening in the irradiated areas. A new layer of photocurable resin is then introduced from the top or bottom of the previous layer, and this layer is hardened by irradiation. The advantages of irradiation-based techniques are the fast photopolymerization process, the high resolution with which light can be applied to each layer, and some flexibility regarding material properties. While stereolithography is a well-known technique, the aforementioned drawbacks still apply. Stereolithography requires support structures, necessitating elaborate post-processing. Despite the fast photopolymerization rate, the slow mechanical process of advancing from one layer to the next reduces the overall production speed of stereolithography. Furthermore, the resin must meet certain criteria, such as low viscosity to allow flow and layer homogeneity, and high absorption at the irradiation wavelength to avoid curing in previous layers. Because thin layers are required for high resolution and low viscosity, oxygen and water concentrations at the surface are high. Water terminates the cationic polymerization process, while oxygen terminates the radical process. While the latter can be improved by adding amines, the resin still requires high concentrations of expensive photoinitiators to overcome the inhibition process, resulting in a material with low crosslinkability and therefore low robustness.

[0011] To overcome the limitations of stereolithography, volumetric printing has been proposed as a solution. In this approach, the resin is contained within a container, and through the action of light, curing occurs within the volume, rather than on the container walls. This eliminates the need for support structures, allows for low- and high-viscosity resins, and allows for the formation of soft objects that are not inhibited by oxygen or water.

[0012] One implementation of volumetric printing relies on two-photon polymerization, in which a common photoinitiator is excited by the simultaneous capture of two photons, inducing polymerization at the focus of a laser beam [S. Maruo et al., Opt. Lett., 1997, 22, 132-134]. Two-photon polymerization requires an expensive and delicate setup and requires a powerful pulsed laser source. Furthermore, this technique is inherently slow due to the nonlinearity of the process, significantly reducing the achievable object size.

[0013] Furthermore, a tomographic reconstruction method has been developed, in which the resin is illuminated with different light patterns from various angles. The overlapping light generates an intensity distribution within the volume, which causes curing everywhere above a certain threshold. The light pattern required to form a 3D object is pre-calculated in a manner similar to the inverse process of computer tomography analysis [Kelly et al., US20180326666A1, 2018; Shusteff et al., US20180015672A1, 2018; Delrot et al., WO2019043529A1, 2019]. This technique has the inherent drawback of matching the curing threshold at every location within the volume. Furthermore, the resin rotates, causing diffusion during curing. Both effects result in low resolution and small object size. Furthermore, this technique is limited to round surfaces of printed parts due to its inability to generate objects with sharp edges.

[0014] To overcome the problems of two-photon polymerization and tomographic reconstruction, a two-color photoinitiator system can be envisioned. This requires a photoinitiator that, upon irradiation with light at a first wavelength (λ1), converts from its thermodynamically stable ground state, Form A, to a metastable ground state, Species B. When Species B absorbs light at a second wavelength (λ2), it can initiate the polymerization reaction via Form C. Form C is an excited state of B, which, with or without a co-initiator, can further react to produce radicals, cations, or anions. In this invention, the terms "first wavelength," "second wavelength," and "third wavelength" can refer to ranges of wavelengths. For use in volumetric printing approaches, the reverse reaction from B to A must be possible to avoid curing undesired regions. The reverse reaction from B to A can be induced thermally or by irradiation with a third wavelength (λ3).

[0015]

number

[0016] There are two undesirable reaction pathways that can lead to polymerization with only the first wavelength: A can directly initiate polymerization instead of switching, or B can absorb photons at the first wavelength and initiate polymerization. An ideal bichromatic photoinitiator suitable for volume printing would not suffer from these undesirable reactions and would be thermally reversible or could be switched back upon irradiation with a third wavelength. The following examples concern photoinitiators and multi-wavelength irradiation, but all of them suffer from undesirable side reactions and / or a lack of thermal reversibility. To date, no three-dimensional objects other than a single voxel have been fabricated, which does not require any thermal or photochemical back reactions, which are not sufficient for volume printing.

[0017] A related concept was first proposed by Swainson in a series of patents [Swainson, US4041476, US4078229, US4238840, US4466080, US4471470, US4333165] and later by Lippert (US2020 / 0108557A1). Several theoretical approaches are presented, in which photoinitiators are assumed to respond to two or three different wavelengths. However, while this concept is intriguing, none of the molecules described in these patents have been shown to respond to two different wavelengths to initiate polymerization, nor are they feasible or commercially viable for volumetric printing.

[0018] JP H0375127A by Kenji and Ichiro claimed three photoswitches for volume printing. The molecules described therein are known for their photochromic properties, but they do not exhibit selective curing; beams of both wavelengths cross, as shown by Neckers [US005230986A, column 6, lines 27-35]. Even if they could be initiated with bichromatic irradiation, they exhibit a slow thermal reverse reaction from B to A, making them unsuitable for volume printing applications.

[0019] Barachevsky et al. [US 7244548 B2, 2007] and Waldman et al. [US 2009 / 0202919 A1] disclosed several initiators for recording phase holograms. In this type of application, a curable composition is first irradiated with one wavelength to induce isomerization from A to B. A second wavelength can then be used to initiate polymerization and record a phase hologram. This application requires a photoinitiator that responds to two different wavelengths but does not exhibit a thermal back-reaction from B to A. The lack of a thermal back-reaction makes the disclosed initiators unsuitable for volume printing approaches.

[0020] US005230986A to Neckers disclosed iodinated benzospiropyrans having the following structure (wherein at least one of the two substituents X1 and X3 is iodine) as two-photon radical photoinitiators, together with a suitable coinitiator:

[0021] [ka]

[0022] The disclosed molecules require high concentrations due to limited photopolymerization efficiency [Lee, Neckers, Chem. Mater. 1991, 3, 852-858 and Lee, Neckers, Chem. Mater. 1991, 3, 858-864]. As a result, as shown by the same authors [Lee, Neckers, Chem. Mater. 1991, 3, 858-864, Figures 12 and 13], the penetration depth of light is limited, and volumes suitable for printing cannot exceed 2 mm. Because the iodo substituent acts as a triplet sensitizer on the spiropyran form, undesired side reactions from irradiation using only the first wavelength dominate, and the spiropyran induces a photoredox reaction, thus forming radicals, without isomerizing to a merocyanine. Iodinated benzospiropyrans are further limited by the slow thermal back-reaction, making them unsuitable for volume printing.

[0023] Two other spiropyran-based two-component systems for recording holograms have been reported [Jeudy, Robillard, Opt. Commun. 1975, 13, 25-28; Ichimura, Sakuragi, J. Polym. Sci. Polym. Lett. 1988, 26, 185-189]. However, neither is suitable for volume printing. This is because, on the one hand, the thermal reverse reaction in both cases is too slow for commercially successful applications, and, on the other hand, both induce substantial polymerization only at the first wavelength [Lee, Neckers, Chem. Mater. 1991, 3, 858-864].

[0024] The present invention aims to overcome the drawbacks of currently available methods. More specifically, it aims to provide a process, apparatus, and photoswitchable photoinitiators for the local polymerization of starting materials by two-color photopolymerization, as well as a method for volume printing of molded objects. These enable flexible and locally targeted curing within the starting material by photopolymerization (xolography). This technology is particularly applicable to 3D printing. More specifically, photoinitiators can be provided that induce curing of photopolymerizable formulations when irradiated with two different wavelengths and can be used for volume printing (xolocure initiators).

[0025] Summary of the Invention For this solution, a process for local polymerization of a starting material by two-color photopolymerization is provided according to independent claims 1 and 21. Furthermore, a process for 3D printing of a shaped body is provided according to claim 20. Further embodiments are the subject of the dependent claims.

[0026] According to one embodiment, a process for localized polymerization of a starting material by two-color photopolymerization is provided. A polymerizable starting material is provided containing photoinitiator molecules that can be converted to a reactive state by sequential photoexcitation at several wavelengths. In this reactive state, the photoinitiator molecules locally induce polymerization of the starting material, particularly localized curing or hardening of the starting material by polymerization. The starting material is photopolymerized in a localized volume by irradiating the localized volume with light at a first wavelength and simultaneously or subsequently irradiating the localized volume with light at a second wavelength different from the first wavelength.

[0027] In the localized volume, the photoinitiator molecules are converted from an initial state, which does not substantially absorb light at a second wavelength, to an intermediate state with different optical properties from the initial state by absorbing photons at a first wavelength. Thus, the photoinitiator molecules in the intermediate state absorb light at a second wavelength and enter a reactive state. Due to the gradual absorption of light at the first wavelength and light at the second wavelength in the localized volume, the photoinitiator molecules transition from the initial state through the intermediate state to the reactive state, inducing polymerization locally. Outside the localized volume, the photoinitiator molecules in the intermediate state return to the initial state.

[0028] According to another aspect, an apparatus for localized polymerization of a starting material by bicolor photopolymerization is provided. The apparatus includes an inlet for polymerizable starting material, a light generating means configured to provide light at a first wavelength and light at a second wavelength different from the first wavelength, and a light directing means configured to irradiate a localized volume with light at the first and second wavelengths. The apparatus is configured to perform the following process: introducing the polymerizable starting material through the inlet; the starting material contains photoinitiator molecules, which can be converted by sequential optical excitation into a reactive state that locally induces polymerization of the starting material, and irradiating the defined localized volume with light at the first and second wavelengths photopolymerizes the starting material in the localized volume. In the localized volume, the photoinitiator molecules are converted from an initial state in which they essentially do not absorb the second light to a metastable intermediate ground state whose optical properties have changed compared to the initial state upon absorption of photons at the first wavelength, such that the photoinitiator molecules in the intermediate state absorb light at the second wavelength. In the localized volume, the photoinitiator molecules are transformed from an initial state through an intermediate state to a reactive state due to the gradual absorption of light at the first and second wavelengths, which locally induces polymerization. Outside the localized volume, the photoinitiator molecules in the intermediate state return to the initial state.

[0029] Further provided is a method for volume printing of a molded body, in which the molded body is produced by a method for local polymerization of a starting material, wherein the local photopolymerization hardens the starting material, thereby producing the molded body.

[0030] The absorption capacity of the photoinitiator molecules in the intermediate state for light at the second wavelength can be based on a change in the optical properties of the photoinitiator molecules, whereby the absorption capacity for light at the second wavelength is first formed, and in particular, a spectral absorption band is formed in the region of the second wavelength upon transition from the initial state to the intermediate state. Alternatively, an absorption band for light at the second wavelength already present in the initial state of the photoinitiator molecules can be amplified or broadened in the intermediate state.

[0031] In the intermediate state, the photoinitiator molecules may or may not still be absorbing in the first wavelength range. More preferably, the photoinitiator molecules in the intermediate state may not substantially absorb light at the first wavelength. Most preferably, the photoinitiator molecules in the intermediate state may not absorb light at the first wavelength.

[0032] In one embodiment, the intermediate state can be thermally restored to the initial state at the printing temperature. More preferably, the intermediate state can be thermally restored to the initial state at k=0.01s. -1 The initial state can be thermally restored at the printing temperature with a rate constant higher than 0.02 s. More preferably, the rate constant of the thermal reverse reaction is 0.02 s. -1 Even more preferably, the rate constant of the thermal reverse reaction is 0.05 s -1 Most preferably, the rate constant of the thermal reverse reaction is 0.08 s -1 Higher.

[0033] In various embodiments, localized photopolymerization in localized areas can harden the starting material.

[0034] The light at the first and second wavelengths can be simultaneously irradiated onto the localized volume.

[0035] The light at the second wavelength can be applied to the localized volume after the light at the first wavelength has finished irradiating the localized volume, and the light at the second wavelength is applied before the end of the decay time of the intermediate state of the photoinitiator molecules.

[0036] Upon absorption of light of the second wavelength, the photoinitiator molecules can be converted to a reactive state, which induces polymerization in the local volume. This reactive state can be intended to be generated similarly to a Norrish Type I or Norrish Type II reaction known to those skilled in the art. Alternatively, this reactive state can be intended to undergo an electron transfer reaction with a coinitiator.

[0037] Further bichromatic photoinitiators are disclosed that respond to electromagnetic radiation of a first wavelength by switching from a thermodynamically stable state A to a metastable state B. B can absorb electromagnetic radiation of a second wavelength, thereby forming form C, which can initiate a polymerization reaction. B can undergo a rapid thermal reverse reaction to form A, after which it becomes inactive to electromagnetic radiation of the second wavelength. Application of such bichromatic photoinitiators enables curing of a photopolymerizable resin in any volume where both wavelengths of electromagnetic radiation intersect, such as where an image is projected onto a light sheet. The disclosed substitution pattern ensures a rapid thermal reverse reaction, preventing curing by the first wavelength alone and preventing curing in undesired areas. Application of the disclosed bichromatic photoinitiators in polymerizable mixtures enables high-speed volumetric printing with high resolution. Support structures are not required, saving materials and enabling the creation of soft, fragile products. High reactivity is achieved because a wide range of possible resin viscosities can be covered and polymerization termination by oxygen and water is minimized. The utilization of the disclosed bichromal photoinitiators allows for faster printing than typical photopolymerization-based additive manufacturing techniques due to less mechanical manipulation.

[0038] The disclosed bichromatic photoinitiators are characterized in that polymerization is induced where two different wavelengths of electromagnetic radiation interact, either simultaneously or sequentially, with the same volume of polymerizable material, and not where the volume interacts with electromagnetic radiation of only one wavelength.

[0039] The disclosed bicolor photoinitiators in thermodynamically stable Form A absorb a photon from electromagnetic radiation at a first wavelength, which induces an isomerization reaction to metastable Form B. The bicolor photoinitiator in metastable Form B absorbs a photon from electromagnetic radiation at a second wavelength, which induces an isomerization reaction to metastable Form B, which induces the formation of a radical by hydrogen abstraction from the coinitiator followed by electron transfer or decomposition to a radical, electron transfer followed by hydrogen abstraction or decomposition to a radical, or homolytic bond cleavage, which may occur before or after other rearrangement reactions to form radicals. A bicolor photoinitiator in metastable State B that has not absorbed a photon from electromagnetic radiation at the second wavelength spontaneously reverts to thermodynamically stable State A via a thermal process.

[0040] The bichromatic photoinitiator possesses a carbonyl functional group, which is a weak triplet sensitizer for spiropyrans and related structures, and therefore does not cure under UV light alone. Electromagnetic radiation at a first wavelength induces excitation of the initiator form A and switching to the initiator form B, primarily via the singlet state. The efficient ring-opening reaction of the photoswitch motif prevents radical formation in the bichromatic initiator upon irradiation with only the first wavelength. The merocyanine-type form B can act as an internal triplet sensitizer upon irradiation with a second wavelength. This allows the carbonyl group to abstract a hydrogen atom from the coinitiator, carrying out an electron transfer reaction, or homolytic bond cleavage. Substituents are selected to minimize or eliminate the absorption of the merocyanine-type form B at the first wavelength, thermodynamically destabilizing the form B to ensure rapid thermal back-reaction from B to A. Additionally, the disclosed bichromal initiators benefit from exceptionally low or negligible quantum yields for the competing photoreaction from B to A, and the high extinction coefficient of form B in a region where form A does not absorb. Merocyanine form B typically has broad absorption in the visible region, which allows for high intensity over a wide range of wavelengths.

[0041] Suitable bicolor photoinitiators have the following structure, represented by formula (I):

[0042] [ka]

[0043] During the ceremony, R a and R b are independently selected from unsubstituted or substituted aryl, or unsubstituted or substituted alkyne, or are joined together to form an unsubstituted or substituted ring structure; Y is selected from O, S, or N; when Y is N, the substituents R are selected from the group consisting of benzimidazole, indoline, indole, dihydroquinoline, and tetrahydroquinoline. 8 Contains the atoms necessary to complete it together; Z is N or CR 4 Selected from; R 3 ~R 8 H; D; halogen; NO2; CN; OH; SH; substituted or unsubstituted C1-C 20 Alkyl; substituted or unsubstituted C3-C 20 Cycloalkyl; substituted or unsubstituted C6-C 48 Aryl; substituted or unsubstituted C2-C 42 Heteroaryl; substituted or unsubstituted C2-C 49 Alkyl acyl; substituted or unsubstituted C2-C 49 Arylacyl; substituted or unsubstituted C1-C 20 Alkoxy; substituted or unsubstituted C6-C 48 Aryloxy; and NH2; substituted or unsubstituted C1-C 20 Alkyl esters; substituted or unsubstituted C6-C 48 Aryl esters; substituted or unsubstituted C1-C 20 Alkylamides; substituted or unsubstituted C6-C 48 Arylamide; NR'2, SiR'3, -O-SiR'3 (wherein R' is a substituted or unsubstituted C1-C 20 Alkyl and substituted or unsubstituted C6-C 48aryl, wherein two R' may form a ring structure); substituted or unsubstituted carboxylic acids and salts thereof; substituted or unsubstituted sulfonic acids and salts thereof; substituted or unsubstituted sulfonic acid esters; substituted or unsubstituted sulfonic acid amides; formyl; ethers, thioethers; carbonates; carbonate esters; sulfates; boronic acids; boronic acid esters; phosphonic acids; phosphonic acid esters; phosphines; phosphates; peroxycarbonates; thiocarbonates; sulfinic acids; sulfinic acid esters; sulfonates; thiol esters; sulfoxides; sulfones; Hydrazides; Thioaldehydes; Ketones; Thioketones; Oximes; Hydrazines; Nitroso; Azo; Diazo; Diazonium; Isocyanides; Cyanates; Isocyanates; Thiocyanates; Isothiocyanates; Hydroperoxides; Peroxides; Acetals; Ketals; Orthoesters; Orthocarbonate Esters; Ammonium; Imines; Imides; Azides; Nitrates; Isonitriles; Nitrosoxy; Substituted or Unsubstituted Carbamates; Substituted or Unsubstituted Ethers; Substituted or Unsubstituted Polyether Carbamates; Substituted or Unsubstituted Arylazo; Substituted or Unsubstituted C2-C 20 Alkynyl and substituted or unsubstituted C2-C 20 alkenyl; R 3 ~R 8 When one or more substituents are present, the one or more substituents are selected from the group consisting of D; halogen; NO; CN; C-C 49 Alkyl acyl; substituted or unsubstituted C1-C 20 Alkoxy; substituted or unsubstituted C6-C 48 Aryloxy; substituted or unsubstituted C2-C 49 independently selected from the group consisting of aryl acylate; (meth)acrylate; tosyl; NH; and OH; and / or R 5 ~R 8 two adjacent groups may be bonded to each other to form a fused ring structure (preferably a fused aromatic C6 ring); R 3 ~R 8At least one of is selected from one of the following structures:

[0044] [ka]

[0045] During the ceremony, R 14 ~R 25 H; D; halogen; NO2; CN; OH; SH; substituted or unsubstituted C1-C 20 Alkyl; substituted or unsubstituted C3-C 20 Cycloalkyl; substituted or unsubstituted C6-C 48 Aryl; substituted or unsubstituted C2-C 42 Heteroaryl; substituted or unsubstituted C2-C 49 Alkyl acyl; substituted or unsubstituted C2-C 49 Arylacyl; substituted or unsubstituted C1-C 20 Alkoxy; substituted or unsubstituted C6-C 48 Aryloxy and NH2; substituted or unsubstituted C1-C 20 Alkyl esters; substituted or unsubstituted C6-C 48 Aryl esters; substituted or unsubstituted C1-C 20 Alkylamides; substituted or unsubstituted C6-C 48 Arylamide; NR'2, SiR'3, -O-SiR'3 (wherein R' is a substituted or unsubstituted C1-C 20 Alkyl and substituted or unsubstituted C6-C 48aryl, wherein two R' may form a ring structure); substituted or unsubstituted carboxylic acids and salts thereof; substituted or unsubstituted sulfonic acids and salts thereof; substituted or unsubstituted sulfonic acid esters; substituted or unsubstituted sulfonic acid amides; formyl; ethers, thioethers; carbonates; carbonate esters; sulfates; boronic acids; boronic acid esters; phosphonic acids; phosphonic acid esters; phosphines; phosphates; peroxycarbonates; thiocarbonates; sulfinic acids; sulfinic acid esters; sulfonates; thiol esters; sulfoxides; sulfones; Hydrazides; Thioaldehydes; Ketones; Thioketones; Oximes; Hydrazines; Nitroso; Azo; Diazo; Diazonium; Isocyanides; Cyanates; Isocyanates; Thiocyanates; Isothiocyanates; Hydroperoxides; Peroxides; Acetals; Ketals; Orthoesters; Orthocarbonate Esters; Ammonium; Imines; Imides; Azides; Nitrates; Isonitriles; Nitrosoxy; Substituted or Unsubstituted Carbamates; Substituted or Unsubstituted Ethers; Substituted or Unsubstituted Polyether Carbamates; Substituted or Unsubstituted Arylazo; Substituted or Unsubstituted C2-C 20 Alkynyl and substituted or unsubstituted C2-C 20 alkenyl; R 14 ~R 25 When one or more substituents are present, the one or more substituents are selected from the group consisting of D; halogen; NO; CN; C-C 49 Alkyl acyl; substituted or unsubstituted C1-C 20 Alkoxy; substituted or unsubstituted C6-C 48 Aryloxy; substituted or unsubstituted C2-C 49 independently selected from the group consisting of aryl acylate; (meth)acrylate; tosyl; NH; and OH; R 15 and R 16 may be linked to each other to form an unsubstituted or substituted ring structure, such as a cyclohexyl ring, a cyclopentyl ring, or a piperidine ring.

[0046] Preferably, a suitable two-color photoinitiator may have the following structure, represented by formula (II):

[0047] [ka]

[0048] During the ceremony, X is S, CR 1 R 2 , or NR 1 Selected from; Y is O, S, or NR c when Y is N, the substituent R c R represents a ring structure selected from the group consisting of benzimidazole, indoline, indole, dihydroquinoline, and tetrahydroquinoline. 8 Contains the atoms necessary to complete it together; Z is N or CR 4 Selected from; R 1 ~R 13 is R in relation to the above formula (I). 3 ~R 8 are selected independently from those defined in

[0049] Preferably, R a and R b Substituted or unsubstituted C6-C 14 Aryl and substituted or unsubstituted C2-C 10 alkynyl. More preferably, R a and R b is independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, and C2-C5 alkynyl.

[0050] Preferably, X is S or CR 1 R 2 More preferably, X is C and R 1 and R 2 can be independently selected from H, D, and C1-C4 alkyl. More preferably, R 1 and R2 is methyl.

[0051] Preferably, Z is CR 4 More preferably, Z is C and R 4 H, D, CN, C1~C 12 Alkyl, fluorinated C1-C 12 Alkyl, or C6-C 14 aryl. More preferably, R 3 and R 4 is H.

[0052] Preferably, R 9 may be selected from H, D, substituted or unsubstituted C1-C4 alkyl, phenyl, and benzyl. More preferably, R 9 is methyl, —CH2—CH2—OH, phenyl or benzyl.

[0053] Preferably, R 10 ~R 13 may be independently selected from H, D, C1-C4 alkyl.

[0054] Preferably, R 14 may be selected from H, methyl, halogen, more preferably R 14 , R 15 and R 16 can be independently selected from H, methyl, and halogen. More preferably, R 14 , R 15 , and R 16 is chlorine.

[0055] Preferably, R 14 , R 15 , and R 16 is H, D, CN, substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C 10 Cycloalkyl; substituted or unsubstituted C6-C 32 Aryl; substituted or unsubstituted C2-C 28 heteroaryl, and more preferably, R14 , R 15 , and R 16 may be selected from methyl, phenyl, or substituted phenyl.

[0056] In a further preferred embodiment, R 14 is NR'2, where R' is H, D, substituted or unsubstituted C1-C 10 Alkyl and substituted or unsubstituted C6-C 32 aryl, and two R' may form a ring structure; R 15 and R 16 is H, D, CN, substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C 10 Cycloalkyl; substituted or unsubstituted C6-C 32 Aryl; substituted or unsubstituted C2-C 28 More preferably, R 14 is NR'2 (wherein R' is a substituted or unsubstituted C1-C 10 alkyl, and two R' may form a ring structure; R 15 and R 16 is a substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C 10 Cycloalkyl; substituted or unsubstituted C6-C 32 aryl. Most preferably, R 14 may be NR'2 (wherein R' may be methyl, ethyl, or two R' completing a morpholine); R 15 and R 16 is independently selected from methyl, ethyl and benzyl.

[0057] In another preferred embodiment, R 14 OR' {wherein R' is H, D, substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C 10 Cycloalkyl; substituted or unsubstituted C6-C32 Aryl; substituted or unsubstituted C2-C 28 Heteroaryl, SiR″3, where R″ is a substituted or unsubstituted C1-C 10 Alkyl and substituted or unsubstituted C6-C 32 aryl)}, and R 15 and R 16 is H, D, CN, substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C 10 Cycloalkyl; substituted or unsubstituted C6-C 32 Aryl; substituted or unsubstituted C2-C 28 More preferably, R is independently selected from the group consisting of: 14 OR' {wherein R' is H, D, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, SiR″3, where R″ is a substituted or unsubstituted C1-C 10 Alkyl and substituted or unsubstituted C6-C 32 R may be independently selected from the group consisting of aryl. 15 and R 16 is a substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C 10 Cycloalkyl; substituted or unsubstituted C6-C 32 aryl. Most preferably, R 14 is OR', where R' is methyl, ethyl, benzyl, or trimethylsilyl; R 15 and R 16 is independently selected from methyl, ethyl, phenyl, and benzyl.

[0058] In a further preferred embodiment, R 14 and R 15 OR', where R' is H, D, substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C10 Cycloalkyl; substituted or unsubstituted C6-C 32 Aryl; substituted or unsubstituted C2-C 28 heteroaryl), and R 16 is H, D, CN, substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C 10 Cycloalkyl; substituted or unsubstituted C6-C 32 Aryl; substituted or unsubstituted C2-C 28 More preferably, R 14 and R 15 OR', where R' is H, D, substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C 10 cycloalkyl); R 16 is a substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C 10 Cycloalkyl; substituted or unsubstituted C6-C 32 aryl. Most preferably, R 14 and R 15 may be OR', where R' is H, methyl, ethyl, or benzyl; R 16 may be selected from methyl, ethyl, phenyl, and benzyl.

[0059] Preferably, R 17 is a substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C 10 Cycloalkyl; substituted or unsubstituted C6-C 32 Aryl; substituted or unsubstituted C2-C 28 Heteroaryl, substituted or unsubstituted C2-C 20 Alkynyl and substituted or unsubstituted C2-C 20 alkenyl, OR' (wherein R' is H, D, substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C 10Cycloalkyl; substituted or unsubstituted C6-C 32 Aryl; substituted or unsubstituted C2-C 28 heteroaryl), and the substituents may be selected from the group consisting of R 5 ~R 8 or R 10 ~R 13 and R 17 is a substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C6-C 32 aryl; OR', where R' is H, substituted or unsubstituted C1-C 10 alkyl). Most preferably, R 17 may be methyl, ethyl, phenyl, methoxy, or ethoxy.

[0060] Preferably, R 18 is O or NR' (wherein R' is a substituted or unsubstituted C1-C 20 Alkyl esters; substituted or unsubstituted C6-C 48 aryl esters). More preferably, R 18 is O or NR' (wherein R' is a substituted or unsubstituted C6-C 48 aryl esters). Most preferably, R 18 may be O or NR', where R' is a phenyl ester or tolyl ester.

[0061] Preferably, R 19 is a substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C 10 Cycloalkyl; substituted or unsubstituted C6-C 32 Aryl; substituted or unsubstituted C2-C 28 Heteroaryl, substituted or unsubstituted C2-C 20 Alkynyl and substituted or unsubstituted C2-C 20alkenyl, and the substituents may be selected from the ring structure forming anthracene, thioxanthone, or fluorenone, R 5 ~R 8 or R 10 ~R 13 and more preferably, R 19 may be selected from substituted or unsubstituted phenyl or naphthyl.

[0062] Preferably, R 20 and R 21 is a substituted or unsubstituted C6-C 32 Aryl; substituted or unsubstituted C2-C 28 heteroaryl, OR' (wherein R' is a substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C 10 Cycloalkyl; substituted or unsubstituted C6-C 32 Aryl; substituted or unsubstituted C2-C 28 heteroaryl), more preferably R 20 and R 21 may be independently selected from phenyl, tolyl, methoxy, and ethoxy.

[0063] Preferably, R 22 , R 23 , and R 24 is H, D, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C6-C 32 Aryl, substituted or unsubstituted C2-C 28 heteroaryl, and more preferably, R 22 , R 23 , and R 24 can be independently selected from methyl, ethyl, or phenyl.

[0064] Preferably, R 25 is a substituted or unsubstituted C6-C32 Aryl; substituted or unsubstituted C2-C 28 heteroaryl, OR' (wherein R' is a substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C 10 Cycloalkyl; substituted or unsubstituted C6-C 32 Aryl; substituted or unsubstituted C2-C 28 heteroaryl); more preferably, R 25 may be selected from phenyl, tolyl, methoxy, and ethoxy.

[0065] Here, the halogen may be fluorine, chlorine, bromine or iodine.

[0066] Here, alkyl, alkenyl, and alkynyl may be cyclic, linear, or branched.

[0067] Here, alkyl acyl has the formula:

[0068] [ka]

[0069] The aryl acylate has the formula:

[0070] [ka]

[0071] In the formula, the wavy line represents the attachment of the acyl group to the structure of formula (I).

[0072] Group R1~R 13 If one (or more) of are selected as amides, the attachment can be via N as well as via CO.

[0073] Group R1~R 13If one (or more) of the following is selected as an ester, the attachment can be via O as well as via CO.

[0074] In one embodiment, R 3 , R 4 , R 8 , R 10 and R 11 is H and R 5 , R 6 , R 7 , R 12 and R 13 One of the C2 to C is substituted or unsubstituted 49 It is an arylacyl.

[0075] In a further embodiment, R 1 and R 2 is C1~C 20 Alkyl, or C1-C 12 alkyl, or C1-C8 alkyl, or C1-C4 alkyl, or methyl.

[0076] In a further embodiment, R 3 ~R 8 and R 10 ~R 13 is H, D, halogen, NO2, CN, substituted or unsubstituted C2-C 49 Alkyl acyl; substituted or unsubstituted C2-C 49 Independently selected from the group consisting of arylacyl, substituted or unsubstituted aryl, NH2, and OH, where one or more substituents, if present, are selected from halogen, NO2, CN, NH2, and OH.

[0077] In a further embodiment, R 3 ~R 8 and R 10 ~R 13 is independently selected from the group consisting of H and electron withdrawing groups.

[0078] base R 1 ~R 13In all embodiments in which one or more of is selected from halogen, it can be provided that the halogen is F (fluorine).

[0079] In one embodiment, R 12 and R 13 may be bonded to each other to form a fused aromatic C6 ring.

[0080] In one embodiment, R 10 ~R 13 two of may be bonded together to form a fused aromatic C6 ring, R 5 ~R 9 one of which is selected from unsubstituted or substituted arylacyl; or unsubstituted or substituted alkylacyl.

[0081] In one embodiment, R 10 ~R 13 are independently selected from the group consisting of H and electron-withdrawing groups; R 5 ~R 8 wherein one of the groups is selected from unsubstituted or substituted aryl acyl; or unsubstituted or substituted alkyl acyl.

[0082] Typical electron-withdrawing groups are CN, F, NO2, ester groups, acyl groups, SO2R, e.g., SO2CF3, SO2Me, or SO2NH2, SF5, NR3 + , pyridinium, halogen, and fluorinated alkyl or aryl, such as CF3.

[0083] In one embodiment, R 5 ~R 8 at least one of R is independently selected from the group consisting of an electron donating group or an alkoxy; 8 is methoxy and R 5 ~R 8 , R 10 ~R 13 At least one of is selected from unsubstituted or substituted aryl acyl or unsubstituted or substituted alkyl acyl.

[0084] Typical electron donating groups may be SH, SR, OH, OR, NH2, NHR and NR2.

[0085] In one particular embodiment, R 6 , R 7 and R 12 is CF3, SO2Me, SO2NH2, CN, F, NO2, C6 aryl, unsubstituted C6 aryl acyl of the formula below

[0086] [ka]

[0087] Dimethoxy-substituted aryl acyl of the following formula:

[0088] [ka]

[0089] Methoxy-substituted aryl acyl of the formula:

[0090] [ka]

[0091] Fluorine-substituted aryl acyl of the following formula:

[0092] [ka]

[0093] Or the following formula:

[0094] [ka]

[0095] and C6 aryl.

[0096] In a further embodiment, R9 is C1-C 20 Alkyl and C6-C 48 Aryl, or C1-C8 alkyl and C6-C 18 Aryl, or C1-C4 alkyl and C6-C 12 It may be provided that the aryl is selected from the group consisting of methyl, benzyl and phenyl.

[0097] In one embodiment, the dichroic photoinitiator may be attached to a polymerizable group, which may be selected from the group consisting of (meth)acrylates, acrylamides, vinyl ethers, and vinyl esters, preferably (meth)acrylates.

[0098] In another embodiment, two or more dichroic photoinitiators may be linked together by a linker group. The chemical bond to the linker group is R 1 ~R 13 Preferably, R 9 may be independently established by

[0099] In a further embodiment, R 10 ~R 13 are independently selected from the group consisting of H and electron-withdrawing groups; R 3 ~R 8 is provided to be independently selected from the group consisting of H and substituents belonging to the formula:

[0100] [ka]

[0101] More specific R 12 is an electron-withdrawing group, and R 6 is a substituted or unsubstituted arylacyl, the arylacyl group may be unsubstituted or may contain electron-withdrawing or electron-donating substituents, such as:

[0102] [ka]

[0103] or may be substituted with R 6 is an α-aminoacyl, α-hydroxyacyl, or α-alkoxyacyl:

[0104] [ka]

[0105] In a further embodiment, R 3 ~R 8 and R 10 ~R 13 are independently selected from the substituents belonging to the formula:

[0106] [ka]

[0107] More specific R 6 and R 12 is a substituted or unsubstituted aryl acyl, or R 6 and R 12 is an α-aminoacyl, α-hydroxyacyl, or α-alkoxyacyl:

[0108] [ka]

[0109] In the formula, R', R 15 , R 16 are independently selected from the group consisting of H, D, unsubstituted or substituted aryl; or unsubstituted or substituted alkyl, more preferably methyl, ethyl, benzyl, phenyl, and tolyl. Two R' may form a ring structure.

[0110] In a further embodiment, the substituent R 3 ~R 8 and R 10 ~R13 is selected from the substituents belonging to the formula:

[0111] [ka]

[0112] In the formula, the substituent R 14 ~R 25 one of which contains an atom of the second photoswitchable group.

[0113] In a further embodiment, the substituent R 1 ~R 13 It may be provided that one of the functional groups contains a functional group that increases the solubility in water. Such functional groups may in particular be ionic functional groups that form salts, such as ammonium or sulfonate; polyethylene glycol; or polar functional groups, such as OH, NH, SONH.

[0114] In one embodiment, R 5 and R 7 are independently selected from the group consisting of H and electron donating groups, more preferably H, methyl, and methoxy; R 6 is of the formula:

[0115] [ka]

[0116] In the formula, R 20 and R 21 or R 25 are independently selected from aryl or alkoxy, more preferably phenyl, ethoxy, methoxy.

[0117] In a further embodiment, R 10 ~R 13 are independently selected from the group consisting of H and electron-withdrawing groups; R 5 ~R 8is independently selected from the group consisting of H and substituents belonging to the formula:

[0118] [ka]

[0119] In the formula, R 14 ~R 15 are independently selected from halide, alkyl or aryl, more preferably chlorine, methyl, ethyl, phenyl, tolyl.

[0120] In particularly preferred embodiments, the photoinitiator molecules used in the process according to the invention comprise one or more of the following compounds 1-80:

[0121] [ka]

[0122] JPEG0007781413000025.jpg197169

[0123] JPEG0007781413000026.jpg196169

[0124] JPEG0007781413000027.jpg181169

[0125] JPEG0007781413000028.jpg218169

[0126] JPEG0007781413000029.jpg222169

[0127] JPEG0007781413000030.jpg238169

[0128] JPEG0007781413000031.jpg196169

[0129] JPEG0007781413000032.jpg224169

[0130] JPEG0007781413000033.jpg200169

[0131] JPEG0007781413000034.jpg95169

[0132] Alternatively, the photoinitiator molecule comprises one or more of the compounds, or the photoinitiator molecule consists of one or more of the compounds.

[0133] According to the present invention, it may be contemplated that two or more of the above-described embodiments may be combined with one another.

[0134] Due to absorption of light of a second wavelength, the photoinitiator molecules can be converted into a reactive state that induces radical polymerization in the local volume.

[0135] The light beam of light at the first wavelength and the light beam of light at the second wavelength may illuminate localized volumes that at least partially overlap.

[0136] The starting material can be polymerized in several local volumes by photopolymerization, and thus three-dimensional objects can be produced in the starting material.

[0137] In conjunction with a device for local polymerization of starting materials, the above-mentioned compounds can be used in a process for local polymerization of starting materials by two-color photopolymerization. The same applies to a process for 3D printing of molded bodies or a method for volumetric printing of molded bodies.

[0138] A formulation suitable for volume printing may contain the following parts by weight: 1 to 99.9999 wt %, preferably 5 to 99.99 wt %, more preferably 20 to 99.9 wt % of a photopolymerizable compound, for example, a monomer; 0-99 wt %, preferably 1-50 wt %, more preferably 3-20 wt % of the co-initiator, if the co-initiator comprises a photopolymerizable group, e.g., an acrylate; 0 to 50 wt %, preferably 1 to 40 wt %, more preferably 3 to 10 wt % of a co-initiator if the co-initiator does not contain a photopolymerizable group; 0.0001 to 20 wt %, preferably 0.001 to 10 wt %, more preferably 0.01 to 5 wt %, and most preferably 0.1 to 1 wt % of a two-color photoinitiator; 0 to 20 wt %, preferably 1 to 10 wt %, more preferably 3 to 5 wt % of an acid or base; 0 to 90 wt. %, preferably 1 to 70 wt. %, more preferably 5 to 50 wt. %, and most preferably 10 to 30 wt. % of other additives, such as organic or inorganic fillers, optical brighteners, inhibitors, chain transfer agents, and the like; and 0 to 80 wt %, preferably 5 to 50 wt %, more preferably 10 to 30 wt % of a solvent.

[0139] All weight ratios are given relative to the weight of the total formulation.

[0140] Typical curing parameters suitable for volume printing may be: Any setup with two different wavelengths of light; Temperature: -20°C to +100°C, preferably 0°C to +60°C, more preferably +20°C to +60°C First wavelength: 250 nm to 500 nm, preferably 300 nm to 450 nm, and ·Second wavelength: 350nm~800nm.

[0141] To prevent the migration and release of residual dichroic initiator and / or its reaction products from the cured product, the following measures are disclosed: (a) Substitution so that the molecular weight exceeds 1000 g / mol (b) Attachment of the initiator to higher molecular weight structures such as oligomers or polymers (c) Functionalization of the initiator with polymerizable groups that are incorporated into the polymer network during curing (including, but not limited to, acrylates, acrylamides, methacrylates, thiols + enes, epoxides, oxiranes, oxetanes, vinyl ethers). The dichroic initiators are disclosed for curing any resin containing molecules with functional groups that can be polymerized via a radical mechanism, including but not limited to acrylates, methacrylates, acrylamides, thiol-enes, and vinyl acetate derivatives.

[0142] The disclosed bicolor photoinitiators enable volumetric printing due to both their tunable thermal reverse reaction and their ability to initiate polymerization only when both wavelengths of light interact with the resin volume. Bicolor initiators are not limited to a specific setup; the following setup can be used to provide an illustrative example demonstrating the need for a thermal reverse reaction: Volumetric printing can be performed in a setup consisting of a light sheet generator, a projector, a vessel with four transparent sides containing resin containing at least one of the disclosed bicolor photoinitiators, and a movable stage for moving either the vessel or the light sheet generator. This setup ensures a faster curing process across the entire volume compared to the point-by-point setup described by Swainson [Swainson, US 4,041,476, US 4,078,229, US 4,238,840, US 4,466,080, US 4,471,470, US 4,333,165]. One layer of the volume is irradiated with electromagnetic radiation of a first wavelength to switch the bicolor photoinitiator from A to B. An image is projected onto that layer from a different direction using electromagnetic radiation of a second wavelength, inducing photopolymerization where the image and layer overlap. After a predetermined time, the electromagnetic radiation of the first wavelength is shifted to the adjacent layer, and the next image is projected onto this layer using electromagnetic radiation of the second wavelength. In the previous layer, further polymerization does not occur due to a rapid thermal reverse reaction to form A, which induces deactivation to the electromagnetic radiation of the second wavelength. After multiple iterative steps, the three-dimensional object is cured in volume and can be removed, or the residual resin can be washed away. The remaining object may then be post-processed.

[0143] In another embodiment of the present invention, a sensitizer may be used to induce switching from A to B. The sensitizer absorbs at a wavelength where both forms A and B of the bichromic initiator exhibit minimal or no absorption. When the sensitizer is excited by electromagnetic radiation at a first wavelength, energy transfer occurs to form A of the bichromic initiator. Form A of the excited bichromic initiator then switches to form B. Form B absorbs electromagnetic radiation at a second wavelength and initiates polymerization via form C. The use of a sensitizer is beneficial when the absorbance at the first wavelength changes during the irradiation process, ensuring uniform switching and curing throughout the entire optical path of the first wavelength. Furthermore, utilizing a sensitizer allows for the application of higher concentrations of bichromic initiator without increasing absorbance at the first wavelength. Sensitizers can also enable larger object sizes due to more uniform curing. Typical sensitizers known in the art can be used, including, but not limited to, derivatives of the following: (a) a transition metal complex, such as a tris(bipyridine) ruthenium complex, a zinc porphyrin complex, an iridium complex, a rhenium complex, or a platinum complex; (b) boron dipyrromethene; (c) iodo- or bromo-substituted organic chromophores, e.g., rose bengal or eosin B; (d) carbonyl compounds, such as naphthalenediimides, acetophenones, anthraquinones, thioxanthones, camphorquinones, benzophenones, diacetyl compounds, coumarins, benzylideneacetones, dibenzylideneacetones; and (e) Polycyclic aromatic compounds, such as anthracene, pyrene, or fullerene.

[0144] Sensitizers according to (d) and (e) are particularly preferred.

[0145] When a Type 2 dual-color initiator is used, the coinitiator can be selected from typical hydrogen or electron donors known in the art, including, but not limited to, derivatives of ethanolamines, aminobenzoic acids, germanes, thiols, alcohols, ethers, thioethers, silanes, phosphines, acetals, dialkylanilines, N-phenylglycines, arylsulfinates, iodonium salts, sulfonium salts, and organic borates.

[0146] The co-initiator may be of high molecular weight, e.g., >1000 g / mol, or may be polymer-bound to prevent migration in the cured mass. The co-initiator may contain a polymerizable group, e.g., an acrylate or methacrylate, that is incorporated into the polymer network during curing to prevent subsequent co-initiator migration. Typical examples are:

[0147] [ka]

[0148] For two-color volumetric printing, it is advantageous to control the viscosity of the resin. For Type 2 initiators, a large amount of co-initiator affects the viscosity of the resin. Therefore, in some cases, it is beneficial to use a specific viscosity co-initiator or a mixture of common low-viscosity and high-viscosity co-initiators. While low-viscosity co-initiators are commercially available, high-viscosity co-initiators are in short supply.

[0149] High-viscosity coinitiators are composed of a high-viscosity moiety and a hydrogen donor moiety. To achieve high viscosity, one structural motif relies on a backbone that cannot geometrically construct sufficient intermolecular interactions to form a solid. High molecular weight restricts motion, resulting in high viscosity. Another structural motif is based on multiple hydrogen bonds, as in urethane-containing mixtures. To ensure sufficient miscibility with the monomer composition on the one hand and high reactivity on the other, the backbone of the coinitiator may have a similar structure to that of the monomer functional group. Therefore, it may be beneficial to use a coinitiator based on a urethane structure in combination with a monomer composition containing a urethane moiety. It may also be beneficial to use a coinitiator based on a bisphenol structure in combination with a monomer composition containing a bisphenol moiety.

[0150] A typical structure of a high viscosity and reactive coinitiator in a bisphenol-containing resin suitable for volume printing is:

[0151] [ka]

[0152] In the formula, R 28 and R 29 may be independently selected from H, D, alkyl, branched alkyl, substituted alkyl, and cycloalkyl, preferably one or both are methyl, ethyl, and / or hydrogen. 26 and R 27 may be independently selected from OH, OD, alkyl ether, aryl ether, ester, or the following structures:

[0153] [ka]

[0154] In the formula, R 30 ~R 35 are independently selected from H, D, alkyl, aryl, and more particularly R30 ~R 35 is selected from methyl, ethyl, ethyl-OH, (—CH—CH—OH), and phenyl; or R 30 and R 31 , R 32 and R 33 , R 34 and R 35 may include atoms necessary to form a ring structure, and more specific examples include, but are not limited to, morpholine, pyrrolidine, piperidine, piperazine, thiomorpholine, thiomorpholine dioxide, indoline, hydroquinoline, azaadamantane, diarylamine, carbazole, phenoxazine, and phenothiazine.

[0155] When the monomer composition is composed of urethane moieties, a typical structure is as follows:

[0156] [ka]

[0157] In the formula, R 36 is selected from substituted or unsubstituted aryl, substituted or unsubstituted alkyl, cyclic alkyl, polyester, and polyether; R 37 and R 38 is independently selected from substituted or unsubstituted aryl, substituted or unsubstituted alkyl, cyclic alkyl, preferably —CH—CH—OH (ethanol), H, D, methyl, butyl, ethylhexyl, and phenyl. 37 may have the following structure:

[0158] [ka]

[0159] In the formula, R 39 and R 40are independently selected from substituted or unsubstituted aryl, substituted or unsubstituted alkyl, cyclic alkyl, preferably —CH—CH—OH (ethanol), H, D, methyl, butyl, ethylhexyl, and phenyl. Alternatively, R 40 R 37 It can also be the same as

[0160] The above coinitiators can be used as mixtures resulting from different degrees of functionalization. Reactivity and viscosity can be controlled by applying the appropriate ratio of backbone precursor (bisphenol diglycidyl ether, bisphenol ethoxylate, diisocyanate) and amine source, where the amine source has at least two reactive functional groups, such as triethanolamine or any diethanolamine.

[0161] A suitable acid may be a weak acid, such as acetic acid, formic acid, benzoic acid, or a strong acid, such as trifluoroacetic acid.

[0162] Suitable bases may be amines such as diisopropylethylamine, triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 2,6-di-tert-butylpyridine, and 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0163] Suitable solvents may be water or ethyl acetate. Formulations suitable for volume printing may preferably be solvent-free.

[0164] Any combination of the embodiments, preferred ranges and / or portions, especially preferred portions of the present invention is especially preferred.

[0165] BRIEF DESCRIPTION OF THE DRAWINGS Further design examples are described below with reference to the drawing figures.

[0166] FIG. 1 shows a schematic diagram of one embodiment of the process according to the present invention.

[0167] FIG. 2 shows a schematic diagram of the process according to the present invention.

[0168] FIG. 3 shows a perspective view of an embodiment of the inventive process shown in FIG.

[0169] FIG. 1 illustrates a schematic diagram of an embodiment of the present invention. A first light source 10 generates light at a first wavelength and irradiates a structure containing a curable composition 14. The assembly is a layered assembly including a light-shielding layer 11 and two transparent layers 12. The assembly further includes a spacer 13. A curable composition 14, which corresponds to a polymerizable starting material and contains one or more photoinitiator molecules according to the present invention, is introduced into the space formed by the two transparent layers 12 and the spacer 13. The layered structure further includes two light-shielding layers 11 arranged such that at least a portion of the curable composition 14 can be irradiated by both the light at the first wavelength generated by the first light source 10 and the light at the second wavelength generated by the second light source 15. The region of the curable composition 14 that can be irradiated by both the light from the first light source 10 and the light from the second light source 15 is cured according to the mechanism described herein.

[0170] 2 and 3 show a further embodiment of the invention in which a portion of the curable composition 24, 34 is cured. The curable composition 24, 34 is simultaneously irradiated by light from both the first light source 20, 30 and the second light source 25, 35 through holes 23, 33 in the light-shielding layer 21, 31, which partially shield the curable composition 24, 34 from the respective light sources 20, 30 and 25, 35. The curable composition 24, 34 is here disposed in a transparent container 22, 32. In this case, it is provided that the light source 20, 30 is arranged perpendicular to the second light source 25, 35. However, in principle, other angles are also provided here according to the invention.

[0171] In one embodiment, a process is provided for the local polymerization of a polymerizable starting material by dichromatic polymerization. In dichromatic polymerization, a photoinitiator molecule (which may also be referred to as a mediator molecule) absorbs photons of light of different wavelengths to convert the photoinitiator molecule from an initial state, via an intermediate state, to a reactive state. This reactive state is suitable for locally initiating or initiating a polymerization reaction in the polymerizable starting material, so that the starting material polymerizes until hardened, particularly in the case of plastics.

[0172] The mediator molecules (hereinafter also referred to as photoinitiator molecules) and their required functionality can be generated in various ways. As an example, the following is provided:

[0173]

number

[0174] Photoinitiators can exist in three different states characterized as follows: Initial state (A): Without light irradiation, the photoinitiator molecules exist in this state.

[0175] Intermediate state (B): The B state is the electronic ground state. The intermediate state is generated from the initial state A by the absorption of light of wavelength λ1. The photoinitiator molecule has a new or stronger absorption band for light of wavelength λ2. Alternatively, the absorption band at λ1 disappears. The photoinitiator molecule returns to the initial state A spontaneously in the absence of light or by absorption of light at wavelength λ3.

[0176] Reaction state (C): ·The reaction state is generated from intermediate state B by absorption of light of wavelength λ2. ·Reactive conditions initiate polymerization reactions in the immediate vicinity of the molecule. · Back reaction to B is not intended.

[0177] Example The functions and effects of the present invention will be described in detail below with reference to specific examples of the present invention. However, these examples are provided only to illustrate the present invention, and the scope of the present invention is not limited thereto.

[0178] synthesis Spiropyran numbering system

[0179] [ka]

[0180] General synthesis of spiropyrans, spirooxazines, spiroimidazoquinolines-indolines, and benzothiazoles (compounds 1–10, 13–21, 28, 29, 31–57, 62, 64, 70, 77, and 78) Indolene (1 mmol) or benzothiazole precursor (1 mmol) is dissolved in ethanol (5 mL). If an indolenium or benzothiazolium salt is used, the salt (1 mmol) and piperidine (1.5 mmol) are dissolved in ethanol (5 mL) and stirred for 15 minutes. Salicylaldehyde (1 mmol) or ortho-nitrosophenol (1 mmol), or 1H-benzo[d]imidazole-4-carbaldehyde (1 mmol) is added, and the mixture is heated to 70 °C until the starting material is consumed. After cooling to room temperature, the product precipitates, or water is added to precipitate the product. The solid is filtered and washed with ethanol or water. If the filtration procedure does not yield a pure product, the aqueous mixture is extracted with dichloromethane. The combined organic layers are dried over anhydrous MgSO4, and the solvent is evaporated under reduced pressure. The solid residue is purified by recrystallization from ethanol or by silica gel column chromatography using an acetone / petroleum ether mixture as the eluent.

[0181] [ka]

[0182] 1H NMR (500 MHz, クロロホルム-d) δ 7.95 (dd, J = 8.6, 1.0 Hz, 1H), 7.86 - 7.76 (m, 4H), 7.64 (d, J = 2.1 Hz, 1H), 7.58 (dd, J = 8.5, 2.2 Hz, 1H), 7.43 (ddd, J = 8.5, 6.7, 1.4 Hz, 1H), 7.28 - 7.23 (m, 1H), 7.16 (t, J = 8.6 Hz, 2H), 7.03 - 6.95 (m, 2H), 6.75 - 6.71 (m, 1H), 5.87 (d, J = 10.3 Hz, 1H), 2.87 (s, 3H), 1.68 (s, 3H), 1.38 (s, 3H). ESI-MS [M+H] + C 30 H 25 FNO2 + Calculated m / z value: 450.186, measured value: 450.197.

[0183]

change

[0184] 1 H NMR (500 MHz, クロロホルム-d) δ 7.83 - 7.77 (m, 2H), 7.64 - 7.57 (m, 2H), 7.51 (dd, J = 8.2, 1.7 Hz, 1H), 7.29 (d, J = 1.7 Hz, 1H), 7.19 - 7.12 (m, 2H), 6.96 (d, J = 10.3 Hz, 1H), 6.77 (d, J = 8.4 Hz, 1H), 6.54 (d, J = 8.2 Hz, 1H), 5.75 (d, J = 10.3 Hz, 1H), 2.82 (s, 3H), 1.32 (s, 3H), 1.19 (s, 3H). ESI-MS [M+H] + C 27 H 22 FN2O2 + Calculated m / z value: 425.166, measured value: 425.172.

[0185]

change

[0186] 1 H NMR (500 MHz, クロロホルム-d) δ 7.80 - 7.74 (m, 2H), 7.74 - 7.68 (m, 2H), 7.58 - 7.52 (m, 1H), 7.50 - 7.44 (m, 2H), 7.12 (ddd, J = 8.1, 7.4, 1.7 Hz, 1H), 7.07 (dd, J = 7.5, 1.7 Hz, 1H), 6.89 (dd, J = 10.2, 0.7 Hz, 1H), 6.85 (td, J = 7.4, 1.1 Hz, 1H), 6.73 (d, J = 7.9 Hz, 1H), 6.50 (d, J = 8.1 Hz, 1H), 5.67 (d, J = 10.1 Hz, 1H), 2.83 (s, 3H), 1.35 (s, 3H), 1.20 (s, 3H). ESI-MS [M+H] + C 26 H 24 NO2 + のm / z calculated value: 382.180, measured value: 382.190.

[0187]

change

[0188] 1H NMR (500 MHz, クロロホルム-d) δ 7.81 - 7.75 (m, 2H), 7.75 - 7.69 (m, 3H), 7.60 (dd, J = 2.3, 0.7 Hz, 1H), 7.58 - 7.53 (m, 1H), 7.51 - 7.46 (m, 2H), 7.21 (d, J = 8.3 Hz, 1H), 6.98 (dd, J = 10.3, 0.8 Hz, 1H), 6.54 (d, J = 8.6 Hz, 1H), 5.92 (d, J = 10.3 Hz, 1H), 2.83 (s, 3H), 1.36 (s, 3H), 1.22 (s, 3H). ESI-MS [M+H] + C 26 H 23 N2O4 + Calculated m / z value: 427.165, measured value: 427.173.

[0189]

change

[0190] 1 H NMR (500 MHz, クロロホルム-d) δ 8.07 - 8.01 (m, 2H), 7.79 - 7.74 (m, 2H), 7.72 (d, J = 7.1 Hz, 2H), 7.59 - 7.53 (m, 1H), 7.48 (dd, J = 8.2, 6.8 Hz, 2H), 6.97 (d, J = 10.3 Hz, 1H), 6.80 (d, J = 8.7 Hz, 1H), 6.55 (d, J = 8.8 Hz, 1H), 5.87 (d, J = 10.3 Hz, 1H), 2.84 (s, 3H), 1.34 (s, 3H), 1.22 (s, 3H). ESI-MS [M+H] + C 26 H 23 N2O4 + Calculated m / z value: 427.165, measured value: 427.172.

[0191]

change

[0192] 1 H NMR (500 MHz, クロロホルム-d) δ 7.81 - 7.75 (m, 2H), 7.75 - 7.69 (m, 2H), 7.58 - 7.51 (m, 3H), 7.51 - 7.46 (m, 2H), 7.42 (dd, J = 8.4, 7.1 Hz, 2H), 7.37 (dd, J = 8.4, 2.3 Hz, 1H), 7.33 - 7.29 (m, 2H), 6.97 (dd, J = 10.2, 0.7 Hz, 1H), 6.81 (d, J = 8.4 Hz, 1H), 6.52 (d, J = 8.1 Hz, 1H), 5.73 (d, J = 10.1 Hz, 1H), 2.86 (s, 3H), 1.39 (s, 3H), 1.22 (s, 3H). ESI-MS [M+H] + C 32 H 28 NO2 + Calculated m / z value: 458.212, measured value: 458.223.

[0193]

change

[0194] 1¹H NMR (500 MHz, salt-mesh-d²) δ 7.81 - 7.76 (m, 2H), 7.61 - 7.56 (m, 2H), 7.21 - 7.14 (m, 3H), 7.08 (ddd, J = 7.3, 1.3, 0.5 Hz, 1H), 6.94 (dd, J = 10.4, 0.7 Hz, 1H), 6.85 (td, J = 7.4, 1.0 Hz, 1H), 6.77 (dt, J = 8.3, 0.7 Hz, 1H), 6.54 (dt, J = 7.8, 0.7 Hz, 1H), 5.80 (d, J = 10.3 Hz, 1H), 2.75 (s, 3H), 1.31 (s, 3H), 1.18 (s, 3H). ESI-MS [M+H] + C 26 H 23 FNO2 + Calculated m / z value: 400.171, measured value: 400.175.

[0195]

change

[0196] 1 ¹H NMR (500 MHz, salt-mesh d²) δ 7.79 - 7.73 (m, 2H), 7.58 (dd, J = 8.5, 2.2 Hz, 1H), 7.47 (d, J = 2.2 Hz, 1H), 7.34 - 7.26 (m, 4H), 7.21 - 7.14 (m, 4H), 7.09 (td, J = 7.7, 1.3 Hz, 1H), 6.89 (td, J = 7.4, 1.0 Hz, 1H), 6.83 (dd, J = 8.5, 0.7 Hz, 1H), 6.74 (dd, J = 10.3, 0.7 Hz, 1H), 6.58 (dt, J = 7.8, 0.7 Hz, 1H), 5.76 (d, J = 10.3 Hz, 1H), 1.53 (s, 3H), 1.38 (s, 3H), 1.27 (s, 3H) ESI-MS [M+H] + C31 H 25 FNO2 + Calculated m / z value: 462.186, measured value: 462.190.

[0197]

change

[0198] 1 H NMR (500 MHz, クロロホルム-d) δ 8.01 (d, J = 2.1 Hz, 1H), 7.97 (dd, J = 8.4, 2.1 Hz, 1H), 7.62 - 7.46 (m, 2H), 7.51 - 7.43 (m, 2H), 7.33 - 7.24 (m, 2H), 7.42 (dd, J = 2.0, 1.0 Hz, 1H), 6.74 (d, J = 8.4 Hz, 1H), 6.77 (d, J = 8.3 Hz, 1H), 6.40 (dd, J = 8.6, 1.0 Hz, 1H), 5.74 (d, J = 8.6 Hz, 1H), 2.86 (s, 3H), 1.28 (s, 3H), 1.19 (s, 3H). ESI-MS [M+H] + C 26 H 23 N2O4 + Calculated m / z value: 427.165, measured value: 427.155.

[0199]

change

[0200] 1¹H NMR (500 MHz, salt-mesh-d²) δ 7.74 (ddd, J = 8.4, 3.1, 1.4 Hz, 4H), 7.70 (d, J = 8.0 Hz, 2H), 7.66 - 7.60 (m, 2H), 7.60 - 7.55 (m, 2H), 7.49 (td, J = 7.5, 7.0, 1.4 Hz, 4H), 6.98 (dd, J = 10.4, 0.7 Hz, 1H), 6.80 (dd, J = 8.2, 0.8 Hz, 1H), 6.57 (dd, J = 8.0, 0.7 Hz, 1H), 5.80 (d, J = 10.2) Hz, 1H), 2.86 (s, 3H), 1.37 (s, 3H), 1.22 (s, 3H). ESI-MS [M+H] + C 33 H 28 NO3 + Calculated m / z value: 486.206, measured value: 486.199.

[0201]

change

[0202] 1 ¹H NMR (500 MHz, salt-mesh-d²) δ 7.59 (d, J = 2.1 Hz, 1H), 7.54 (dd, J = 8.5, 2.2 Hz, 1H), 7.50 (dd, J = 8.2, 1.7 Hz, 1H), 7.32 - 7.27 (m, 2H), 6.96 (dd, J = 10.3, 0.7 Hz, 1H), 6.70 (dd, J = 8.5, 0.6 Hz, 1H), 6.60 - 6.52 (m, 3H), 5.73 (d, J = 10.3 Hz, 1H), 3.86 (s, 3H), 3.71 (s, 3H), 2.81 (s, 3H), 1.30 (s, 3H), 1.17 (s, 3H). ESI-MS [M+H] + C 29 H 27 N2O4 +のm / z calculated value: 467.197, measured value: 467.215.

[0203]

change

[0204] 1 ¹H NMR (500 MHz, salt-mesh-d²) δ 7.86 - 7.76 (m, 2H), 7.64 (d, J = 2.1 Hz, 1H), 7.58 - 7.47 (m, 2H), 7.47 - 7.35 (m, 5H), 7.17 (dd, J = 8.4, 2.2 Hz, 1H), 6.88 - 6.85 (m, 2H), 6.48 (dd, J = 8.6, 0.9 Hz, 1H), 6.38 (d, J = 2.4 Hz, 1H), 5.84 (d, J = 8.8 Hz, 1H), 3.85 (s, 3H), 3.71 (s, 3H) 2.87 (s, 3H), 1.43 (s, 3H), 1.14 (s, 3H). ESI-MS [M+H] + C 35 H 32 NO5 + Calculated m / z value: 546.227, measured value: 546.236.

[0205]

change

[0206] 1H NMR (500 MHz, Torotron-d8) δ 7.51 (d, J = 2.1 Hz, 1H), 7.48 (dd, J = 8.8, 5.5 Hz, 2H), 7.35 (ddd, J = 8.4, 5.0, 2.0 Hz, 2H), 7.31 (d, J = 1.7 Hz, 1H), 6.66 (t, J = 8.6 Hz, 2H), 6.45 - 6.40 (m, 1H), 6.33 (dd, J = 10.3, 0.7 Hz, 1H), 5.95 (d, J = 8.1 Hz, 1H), 5.26 (d, J = 10.2 Hz, 1H), 2.43 (s, 3H), 1.10 (s, 3H), 0.87 (s, 3H). ESI-MS [M+H] + C 26 H 22 FINO2 + Calculated m / z value: 526.369, measured value: 526.354.

[0207]

change

[0208] 1 H NMR (500 MHz, クロロホルム-d6) δ 7.69 (d, J = 2.2 Hz, 1H), 7.61 (dd, J = 8.8, 5.5 Hz, 2H), 7.51 (ddd, J = 8.1, 1.9, 0.9 Hz, 1H), 7.47 (d, J = 1.8 Hz, 1H), 7.44 (dd, J = 8.4, 2.2 Hz, 1H), 6.76 (s, 1H), 6.55 (d, J = 8.4 Hz, 1H), 6.39 (d, J = 10.2 Hz, 1H), 6.22 (d, J = 8.1 Hz, 1H), 5.30 (d, J = 10.3 Hz, 1H), 2.52 (s, 3H), 1.23 (s, 3H), 0.95 (s, 3H). ESI-MS [M+H] + C 27 H 22 F4NO2+ のm / z calculated value: 468.158, measured value: 468.150.

[0209]

change

[0210] 1 H NMR (500 MHz, クロロホルム-d) δ 7.75 - 7.70 (m, 2H), 7.61 - 7.55 (m, 2H), 7.54 - 7.49 (m, 1H), 7.42 (t, J = 7.6 Hz, 2H), 7.25 (s, 3H), 7.22 - 7.16 (m, 1H), 7.08 (dd, J = 7.3, 1.3 Hz, 1H), 7.06 - 6.98 (m, 2H), 6.85 - 6.78 (m, 2H), 6.74 (d, J = 8.4 Hz, 1H), 6.28 (d, J = 7.7 Hz, 1H), 5.79 (d, J = 10.3 Hz, 1H), 4.55 - 4.46 (m, 1H), 4.16 (d, J = 16.5 Hz, 1H), 1.33 (s, 3H), 1.26 (s, 3H). ESI-MS [M+H] + C 32 H 28 NO2 + Calculated m / z value: 458.211, measured value: 458.223.

[0211]

change

[0212] 1H NMR (500 MHz, クロロホルム-d) δ 7.70 - 7.64 (m, 3H), 7.61 (d, J = 2.1 Hz, 1H), 7.54 (dd, J = 8.4, 1.8 Hz, 1H), 7.27 (dd, J = 1.9, 1.1 Hz, 1H), 7.18 - 7.05 (m, 2H), 6.85 (d, J = 8.4 Hz, 1H), 6.71 (d, J = 8.5 Hz, 1H), 6.43 (dd, J = 8.6, 1.0 Hz, 1H), 5.86 (d, J = 8.5 Hz, 1H), 2.99 (s, 3H), 2.83 (s, 3H), 1.28 (s, 3H), 1.14 (s, 3H). ESI-MS [M+H] + C 27 H 25 FNO4S + Calculated m / z value: 478.148, measured value: 478.122.

[0213]

change

[0214] 1 H NMR (400 MHz, クロロホルム-d) δ 7.65 - 7.58 (m, 3H), 7.48 (dd, J = 8.3, 2.1 Hz, 1H), 7.44 (dd, J = 8.3, 2.0 Hz, 1H), 7.32 (dd, J = 1.8, 1.1 Hz, 1H), 7.15 - 7.09 (m, 2H), 6.78 (d, J = 8.3 Hz, 1H), 6.65 - 6.50 (m, 2H), 6.31 (dd, J = 8.5, 1.0 Hz, 1H), 6.28 (d, J = 9.7 Hz, 1H), 5.89 (d, J = 8.7 Hz, 1H), 2.96 (s, 3H), 1.26 (s, 3H), 1.18 (s, 3H). ESI-MS [M+H] + C 26 H 24 FN2O4S+ Calculated m / z value: 479.144, measured value: 479.163.

[0215]

change

[0216] 1 ¹H NMR (400 MHz, salt-mesh-d²) δ 9.40 (s, 1H), 7.73 - 7.66 (m, 2H), 7.48 - 7.41 (m, 1H), 7.40 - 7.35 (m, 2H), 7.25 - 7.17 (m, 2H), 7.12 - 7.04 (m, 2H), 6.77 (td, J = 7.8, 1.4 Hz, 1H), 6.62 (dd, J = 7.7, 1.4 Hz, 1H), 6.38 (dd, J = 8.7, 1.0 Hz, 1H), 5.82 (d, J = 8.7 Hz, 1H), 2.90 (s, 3H), 1.31 (s, 3H), 1.09 (s, 3H). ESI-MS [M+H] + C 26 H 24 NO3 + のm / z calculated value: 398.175, measured value: 398.189.

[0217]

change

[0218] 1¹H NMR (500 MHz, salt-mesh-d²) δ 8.99 (s, 1H), 7.70 - 7.63 (m, 2H), 7.52 - 7.44 (m, 1H), 7.40 - 7.32 (m, 2H), 7.23 (dd, J = 8.0, 1.4 Hz, 1H), 7.05 - 6.97 (m, 1H), 6.72 (d, J = 1.0 Hz, 1H), 6.65 (td, J = 7.8, 1.5 Hz, 1H), 6.54 (dd, J = 7.8, 1.5 Hz, 1H), 6.45 (dd, J = 8.6, 1.0 Hz, 1H), 5.82 (d, J = 8.6 Hz, 1H), 2.86 (s, 3H), 1.29 (s, 3H), 1.11 (s, 3H). ESI-MS [M+H] + C 26 H 24 NO4 + Calculated m / z value: 414.170, measured value: 414.161.

[0219]

change

[0220] 1 H NMR (500 MHz, クロロホルム-d) δ 7.51 (dd, J = 1.8, 1.0 Hz, 1H), 7.47 - 7.43 (m, 1H), 7.28 (d, J = 2.2 Hz, 1H), 7.25 - 7.17 (m, 4H), 7.15 (dd, J = 8.3, 2.2 Hz, 1H), 7.14 - 7.09 (m, 1H), 6.59 (dd, J = 8.4, 6.7 Hz, 2H), 6.30 (dd, J = 8.6, 1.0 Hz, 1H), 5.87 (d, J = 8.9 Hz, 1H), 3.36 (s, 6H), 2.81 (s, 3H), 1.29 (s, 3H), 1.17 (s, 3H). ESI-MS [M+H] + C 30 H 29 F3NO4+ のm / z calculated value: 524.204, measured value: 524.216.

[0221]

change

[0222] 1 H NMR (400 MHz, クロロホルム-d) δ 7.58 (dd, J = 8.1, 1.8 Hz, 2H), 7.51 (dd, J = 1.8, 1.1 Hz, 2H), 7.48 - 7.42 (m, 6H), 7.29 - 7.21 (m, 6H), 7.32 - 7.28 (m, 2H), 6.66 (dd, J = 8.5, 3.4 Hz, 4H), 6.50 (dd, J = 8.6, 1.0 Hz, 2H), 5.77 (d, J = 8.5 Hz, 2H), 5.61 (s, 1H), 3.28 (s, 3H), 2.77 (s, 3H), 1.29 (s, 3H), 1.08 (s, 3H). ESI-MS [M+H] + C 29 H 27 F3NO3 + Calculated m / z value: 494.194, measured value: 494.181.

[0223]

change

[0224] 1H NMR (400 MHz, クロロホルム-d) δ 7.48 (dd, J = 8.3, 2.1 Hz, 1H), 7.41 (dd, J = 2.0, 1.0 Hz, 1H), 7.35 (d, J = 2.2 Hz, 1H), 7.17 (dd, J = 8.4, 2.1 Hz, 1H), 6.75 (d, J = 8.3 Hz, 1H), 6.65 (d, J = 8.5 Hz, 1H), 6.41 (dd, J = 8.7, 1.0 Hz, 1H), 5.79 (d, J = 8.8 Hz, 1H), 3.79 (s, 3H), 2.79 (s, 3H), 1.21 (s, 3H), 1.11 (s, 3H). ESI-MS [M+H] + C 23 H 21 F3NO4 + Calculated m / z value: 432.142, measured value: 432.151.

[0225]

change

[0226] 1 H NMR (500 MHz, クロロホルム-d) δ 7.60 - 7.55 (m, 2H), 7.47 - 7.41 (m, 1H), 7.40 - 7.34 (m, 2H), 7.18 - 7.07 (m, 2H), 6.98 (dd, J = 7.8, 1.1 Hz, 1H), 6.88 (td, J = 7.5, 1.1 Hz, 1H), 6.75 (dd, J = 7.5, 1.5 Hz, 1H), 6.64 (d, J = 8.7 Hz, 1H), 6.52 - 6.43 (m, 2H), 5.81 (d, J = 8.7 Hz, 1H), 2.81 (s, 3H), 1.27 (s, 3H), 1.19 (s, 3H). ESI-MS [M+H] + C 26 H 24 NO2 +のm / z calculated value: 382.180, measured value: 382.162.

[0227]

change

[0228] 1 H NMR (500 MHz, クロロホルム-d) δ 7.75 - 7.64 (m, 2H), 7.49 - 7.41 (m, 1H), 7.39 - 7.31 (m, 2H), 7.21 - 7.10 (m, 2H), 7.08 - 7.00 (m, 2H), 6.88 (td, J = 7.5, 1.2 Hz, 1H), 6.57 - 6.47 (m, 2H), 6.34 (dd, J = 8.5, 1.0 Hz, 1H), 5.89 (d, J = 8.7 Hz, 1H), 2.87 (s, 3H), 1.20 (s, 2H), 1.15 (s, 2H). ESI-MS [M+H] + C 26 H 24 NO2 + のm / z calculated value: 382.180, measured value: 382.184.

[0229]

change

[0230] 1H NMR (500 MHz, ベンゼン-d6) δ 8.45 (dd, J = 2.3, 1.1 Hz, 1H), 7.96 (dd, J = 8.4, 1.3 Hz, 2H), 7.89 (dd, J = 8.6, 2.2 Hz, 1H), 7.28 (dd, J = 7.6, 1.4 Hz, 1H), 7.25 - 7.22 (m, 1H), 7.09 - 7.01 (m, 2H), 6.98 (ddd, J = 7.3, 3.6, 1.1 Hz, 2H), 6.94 - 6.89 (m, 2H), 6.67 (d, J = 8.5 Hz, 1H), 6.60 (d, J = 7.7 Hz, 1H), 6.41 (d, J = 7.8 Hz, 1H), 2.68 (d, J = 37.5 Hz, 3H), 1.53 (d, J = 25.3 Hz, 3H), 1.38 (d, J = 61.9 Hz, 3H). ESI-MS [M+H] + C 27 H 24 NO3 + のm / z calculated value: 410.175, measured value: 410.188.

[0231]

change

[0232] 1 H NMR (500 MHz, クロロホルム-d) δ 7.79 - 7.74 (m, 2H), 7.72 - 7.65 (m, 3H), 7.57 - 7.52 (m, 1H), 7.47 (dd, J = 8.2, 6.8 Hz, 2H), 7.29 (dd, J = 7.5, 1.6 Hz, 1H), 6.96 (d, J = 10.3 Hz, 1H), 6.91 (dd, J = 8.3, 7.5 Hz, 1H), 6.51 (d, J = 8.2 Hz, 1H), 5.85 (d, J = 10.3 Hz, 1H), 2.83 (s, 3H), 1.40 (s, 3H), 1.22 (s, 3H). ESI-MS [M+H] + C 26 H 23 N2O4 + Calculated m / z value: 427.165, measured value: 427.154.

[0233]

change

[0234] 1 H NMR (400 MHz, クロロホルム-d) δ 7.69 - 7.60 (m, 2H), 7.57 - 7.47 (m, 2H), 7.43 - 7.33 (m, 3H), 7.00 (dd, J = 9.0, 1.0 Hz, 1H), 6.73 (d, J = 8.5 Hz, 1H), 6.43 (dd, J = 9.1, 2.4 Hz, 1H), 6.30 (dd, J = 8.6, 1.0 Hz, 1H), 6.17 (d, J = 2.4 Hz, 1H), 5.70 (d, J = 8.5 Hz, 1H), 3.73 (s, 3H), 2.91 (s, 3H), 1.33 (s, 3H), 1.25 (s, 3H). ESI-MS [M+H] + C 27 H 26 NO3 + Calculated m / z value: 412.191, measured value: 412.184.

[0235]

change

[0236] 1H NMR (500 MHz, クロロホルム-d) δ 8.04 (d, J = 8.5 Hz, 1H), 7.82 - 7.71 (m, 4H), 7.64 (dd, J = 9.7, 5.0 Hz, 2H), 7.62 - 7.57 (m, 1H), 7.57 - 7.43 (m, 3H), 7.35 (ddd, J = 8.0, 6.8, 1.1 Hz, 1H), 6.99 (d, J = 8.8 Hz, 1H), 6.89 (d, J = 8.1 Hz, 1H), 6.51 (d, J = 8.2 Hz, 1H), 5.79 (d, J = 10.4 Hz, 1H), 2.84 (s, 3H), 1.38 (s, 3H), 1.25 (s, 3H). ESI-MS [M+H] + C 30 H 26 NO2 + Calculated m / z value: 432.196, measured value: 432.201.

[0237]

change

[0238] 1 H NMR (500 MHz, クロロホルム-d) δ 7.73 - 7.60 (m, 2H), 7.62 - 7.54 (m, 2H), 7.50 - 7.39 (m, 3H), 6.95 (d, J = 8.5 Hz, 1H), 6.80 - 6.59 (m, 3H), 6.30 (dd, J = 8.6, 0.9 Hz, 1H), 5.69 (d, J = 8.6 Hz, 1H), 3.64 (s, 3H), 2.80 (s, 3H), 1.43 (s, 3H), 1.19 (s, 3H). ESI-MS [M+H] + C 27 H 26 NO3 + Calculated m / z value: 412.191, measured value: 412.184.

[0239]

change

[0240] 1 H NMR (500 MHz, クロロホルム-d) δ 7.97 (d, J = 8.3 Hz, 2H), 7.77 (m, 2H), 7.76 - 7.72 (m, 3H), 7.41 (d, J = 8.6 Hz, 2H), 7.38 (d, J = 4.7 Hz, 2H), 7.20 (m, 2H), 7.06 - 6.98 (m, 1H), 6.51 (d, J = 8.1 Hz, 1H), 5.71 (d, J = 10.1 Hz, 1H), 2.82 (s, 3H), 1.37 (s, 3H), 1.26 (s, 3H). ESI-MS [M+H] + C 30 H 26 NO2 + のm / z calculated value: 432.196, measured value: 432.203.

[0241]

change

[0242] 1 ¹H NMR (500 MHz, salt-mech-d²) δ 7.75 - 7.71 (m, 2H), 7.70 - 7.65 (m, 2H), 7.60 - 7.54 (m, 1H), 7.51 - 7.45 (m, 2H), 7.42 - 7.36 (m, 2H), 6.85 (dd, J = 10.3, 0.7 Hz, 1H), 6.52 (dd, J = 8.2, 7.2 Hz, 2H), 5.74 (d, J = 10.2 Hz, 1H), 2.82 (s, 3H), 1.32 (s, 3H), 1.19 (s, 3H). ESI-MS [M+H] + C 26 H 23 INO2 + Calculated m / z value: 508.077, measured value: 508.069.

[0243]

change

[0244] 1 ¹H NMR (500 MHz, salt-mech-d²) δ 7.86 (d, J = 2.0 Hz, 1H), 7.76 - 7.67 (m, 4H), 7.59 - 7.54 (m, 1H), 7.51 - 7.45 (m, 2H), 7.39 (d, J = 2.0 Hz, 1H), 6.78 (d, J = 10.2 Hz, 1H), 6.60 - 6.53 (m, 1H), 5.76 (d, J = 10.1 Hz, 1H), 2.79 (s, 3H), 1.34 (s, 3H), 1.21 (s, 3H). ESI-MS [M+H] + C 26 H 22 I2NO2 + Calculated m / z value: 633.973, measured value: 633.971.

[0245]

change

[0246] 1 ¹H NMR (500 MHz, salt-mesh-d²) δ 7.76 (dd, J = 8.3, 1.7 Hz, 1H), 7.74 - 7.71 (m, 3H), 7.62 (d, J = 1.7 Hz, 1H), 7.59 - 7.53 (m, 3H), 7.48 (dd, J = 8.2, 6.8 Hz, 2H), 7.42 (dt, J = 7.5, 1.0 Hz, 1H), 7.33 (s, 1H), 7.27 (t, J = 7.7 Hz, 1H), 6.66 (d, J = 8.2 Hz, 1H), 2.89 (s, 3H), 1.42 (s, 3H) 0.72 (s, 3H). ESI-MS [M+H] + C27 H 24 N3O + Calculated m / z value: 406.191, measured value: 406.202.

[0247]

change

[0248] 1 H NMR (500 MHz, クロロホルム-d) δ 8.09 - 8.02 (m, 1H), 7.78 - 7.70 (m, 4H), 7.64 - 7.57 (m, 3H), 7.54 - 7.45 (m, 5H), 7.20 (d, J = 8.2 Hz, 1H), 6.97 (d, J = 8.3 Hz, 1H), 2.80 (s, 3H), 1.26 (s, 3H), 1.12 (s, 3H). ESI-MS [M+H] + C 29 H 25 N2O2 + Calculated m / z value: 433.191, measured value: 433.196.

[0249]

change

[0250] 1 ¹H NMR (500 MHz, salt-mech-d²) δ 7.95 (s, 1H), 7.70 - 7.63 (m, 2H), 7.54 - 7.45 (m, 2H), 7.42 - 7.34 (m, 2H), 7.30 (d, J = 1.7 Hz, 1H), 7.22 (dd, J = 7.8, 1.6 Hz, 1H), 7.02 (td, J = 7.4, 1.6 Hz, 1H), 6.91 (d, J = 8.4 Hz, 1H), 6.85 - 6.73 (m, 2H), 2.85 (s, 3H), 1.39 (s, 3H), 1.24 (s, 3H). ESI-MS [M+H] + C25 H 23 N2O2 + Calculated m / z value: 383.175, measured value: 383.169.

[0251]

change

[0252] 1 H NMR (400 MHz, クロロホルム-d) δ 8.95 (s, 1H), 7.75 - 7.68 (m, 3H), 7.51 - 7.44 (m, 2H), 7.37 - 7.31 (m, 3H), 7.14 - 7.06 (m, 2H), 6.97 (d, J = 8.5 Hz, 1H), 2.86 (s, 3H), 1.31 (s, 3H), 1.14 (s, 3H). ESI-MS [M+H] + C 27 H 23 FN3O + のm / z calculated value: 424.182, measured value: 424.199.

[0253]

change

[0254] 1 H NMR (500 MHz, クロロホルム-d) δ 8.11 - 8.06 (m, 1H), 7.93 - 7.90 (m, 2H), 7.81 - 7.74 (m, 3H), 7.44 - 7.37 (m, 2H), 7.35 - 7.22 (m, 5H), 6.75 (d, J = 8.3 Hz, 1H), 3.78 (s, 3H), 2.91 (s, 3H), 1.31 (s, 3H), 1.16 (s, 3H). ESI-MS [M+H] + C 31 H 27 N2O4 + のm / z calculated value: 491.197, measured value: 491.192.

[0255]

change

[0256] 1 H NMR (500 MHz, クロロホルム-d) δ 7.75 - 7.71 (m, 2H), 7.51 - 7.37 (m, 5H), 6.92 (d, J = 8.3 Hz, 1H), 6.47 - 6.39 (m, 2H), 6.40 - 6.31 (m, 2H), 5.86 (d, J = 8.6 Hz, 1H), 3.60 - 3.32 (m, 4H), 2.87 (s, 3H), 1.30 (s, 3H), 1.24 (s, 3H), 1.21 (t, J = 7.1 Hz, 6H). ESI-MS [M+H] + C 30 H 33 N2O2 + Calculated m / z value: 453.254, measured value: 453.256.

[0257]

change

[0258] 1H NMR (500 MHz, クロロホルム-d) δ 8.07 - 7.99 (m, 1H), 7.76 - 7.68 (m, 2H), 7.60 - 7.55 (m, 1H), 7.49 (td, J = 7.3, 1.9 Hz, 1H), 7.23 (dd, J = 7.8, 2.4 Hz, 1H), 6.97 (d, J = 10.4 Hz, 1H), 6.80 (d, J = 8.8 Hz, 1H), 6.59 (t, J = 8.6 Hz, 1H), 6.54 (d, J = 8.0 Hz, 1H), 5.86 (d, J = 10.3 Hz, 1H), 2.83 (s, 3H), 2.35 (s, 3H), 2.33 (s, 3H), 1.33 (s, 3H), 1.22 (s, 3H). ESI-MS [M+H] + C 28 H 27 N2O4 + Calculated m / z value: 455.197, measured value: 455.185.

[0259]

change

[0260] 1 H NMR (500 MHz, クロロホルム-d) δ 7.69 - 7.59 (m, 2H), 7.55 (d, J = 1.7 Hz, 1H), 7.49 (dd, J = 8.3, 1.8 Hz, 1H), 7.15 (t, J = 8.2 Hz, 2H), 7.06 - 6.99 (m, 2H), 6.80 (d, J = 8.5 Hz, 1H), 6.61 - 6.52 (m, 1H), 6.47 (dd, J = 8.6, 1.0 Hz, 1H), 5.80 (d, J = 8.6 Hz, 1H), 2.90 (s, 3H), 1.31 (s, 3H), 1.18 (s, 3H), 1.11 (s, 9H). ESI-MS [M+H] + C 30 H 31 FNO2+ Calculated m / z value: 456.233, measured value: 456.240.

[0261]

change

[0262] 1 H NMR (500 MHz, ベンゼン-d6) δ 7.94 (d, J = 1.7 Hz, 1H), 7.66 (dd, J = 8.1, 1.8 Hz, 1H), 7.61 (dd, J = 8.7, 5.6 Hz, 2H), 6.85 (td, J = 7.8, 1.7 Hz, 1H), 6.79 (dd, J = 7.7, 1.7 Hz, 1H), 6.71 (t, J = 8.7 Hz, 2H), 6.69 - 6.64 (m, 2H), 6.42 (d, J = 10.2 Hz, 1H), 6.19 (d, J = 8.1 Hz, 1H), 5.27 (d, J = 10.2 Hz, 1H), 2.51 (s, 3H), 1.24 (s, 3H), 0.96 (s, 3H). ESI-MS [M+H] + C 26 H 23 FNO2 + Calculated m / z value: 400.171, measured value: 400.175.

[0263]

change

[0264] 1H NMR (500 MHz, Torotron-d8) δ 10.40 (s, 1H), 7.93 (dd, J = 15.6, 2.1 Hz, 2H), 7.75 (d, J = 6.8 Hz, 1H), 7.68 (dd, J = 8.1, 1.7 Hz, 1H), 7.19 - 7.15 (m, 1H), 7.13 (dd, J = 6.0, 1.4 Hz, 2H), 7.11 (m, 1H), 7.08 (d, J = 2.5 Hz, 1H), 6.40 (d, J = 10.3 Hz, 1H), 6.13 (d, J = 8.1 Hz, 1H), 5.29 (d, J = 10.3 Hz, 1H), 2.44 (s, 3H), 1.13 (m, J = 2.1 Hz, 12H), 0.93 (s, 3H). ESI-MS [M+H] + C 31 H 31 NO3 + Calculated m / z value: 465.230, measured value: 465.241.

[0265]

change

[0266] 1 H NMR (500 MHz, クロロホルム-d) δ 7.79 - 7.74 (m, 2H), 7.73 - 7.67 (m, 2H), 7.59 - 7.53 (m, 1H), 7.51 - 7.45 (m, 2H), 6.88 (dd, J = 10.0, 8.6 Hz, 1H), 6.79 (dd, J = 10.2, 0.6 Hz, 1H), 6.56 (dd, J = 11.2, 6.7 Hz, 1H), 6.51 (dd, J = 7.9, 0.8 Hz, 1H), 5.70 (d, J = 10.2 Hz, 1H), 2.81 (s, 3H), 1.34 (s, 3H), 1.19 (s, 3H). ESI-MS [M+H] + C 26 H 22 F2NO2+ のm / z calculated value: 418.161, measured value: 418.169.

[0267]

change

[0268] 1 H NMR (500 MHz, クロロホルム-d) δ 7.68 (s, 1H), 7.64 - 7.56 (m, 3H), 7.46 - 7.39 (m, 2H), 7.35 (t, J = 7.5 Hz, 2H), 6.77 (d, J = 10.3 Hz, 1H), 6.44 (d, J = 8.1 Hz, 1H), 5.68 (d, J = 10.3 Hz, 1H), 3.80 (s, 3H), 2.67 (s, 3H), 1.22 (s, 3H), 1.10 (s, 3H). ESI-MS [M+H] + C 27 H 24 IN2O5 + Calculated m / z value: 583.072, measured value: 583.084.

[0269]

change

[0270] 1 H NMR (500 MHz, クロロホルム-d) δ 7.79 - 7.74 (m, 2H), 7.70 (d, J = 1.6 Hz, 1H), 7.67 (dd, J = 8.1, 1.8 Hz, 1H), 7.55 - 7.51 (m, 1H), 7.49 - 7.43 (m, 2H), 7.23 (d, J = 3.1 Hz, 1H), 6.93 - 6.85 (m, 2H), 6.50 (d, J = 8.2 Hz, 1H), 5.88 (d, J = 10.3 Hz, 1H), 3.79 (s, 3H), 2.81 (s, 3H), 1.38 (s, 3H), 1.21 (s, 3H). ESI-MS [M+H] + C 27 H 25 N2O5 + Calculated m / z value: 457.176, measured value: 457.168.

[0271]

change

[0272] 1 H NMR (500 MHz, クロロホルム-d) δ 7.83 (s, 1H), 7.77 - 7.73 (m, 2H), 7.73 - 7.70 (m, 2H), 7.58 - 7.53 (m, 1H), 7.50 - 7.45 (m, 2H), 6.91 - 6.85 (m, 1H), 6.55 (d, J = 8.1 Hz, 1H), 6.41 (s, 1H), 5.72 (d, J = 10.3 Hz, 1H), 3.86 (s, 3H), 2.84 (s, 3H), 1.34 (s, 3H), 1.21 (s, 3H). ESI-MS [M+H] + C 27 H 25 N2O5 + Calculated m / z value: 457.176, measured value: 457.165.

[0273]

change

[0274] 1H NMR (500 MHz, クロロホルム-d) δ 7.74 - 7.67 (m, 3H), 7.65 (dd, J = 8.1, 1.8 Hz, 1H), 7.54 - 7.49 (m, 1H), 7.48 - 7.41 (m, 2H), 7.32 (d, J = 2.3 Hz, 1H), 6.99 (d, J = 2.3 Hz, 1H), 6.82 (d, J = 10.2 Hz, 1H), 6.47 (d, J = 8.2 Hz, 1H), 5.66 (d, J = 10.1 Hz, 1H), 2.79 (s, 3H), 1.33 (s, 3H), 1.25 (s, 9H), 1.18 (s, 3H). ESI-MS [M+H] + C 30 H 31 BrNO2 + のm / z calculated value: 516.153, measured value: 516.171.

[0275]

change

[0276] 1 H NMR (500 MHz, クロロホルム-d) δ 7.71 (td, J = 4.3, 1.8 Hz, 2H), 7.59 (d, J = 1.8 Hz, 1H), 7.51 (dd, J = 7.7, 1.8 Hz, 1H), 7.23 (d, J = 7.7 Hz, 1H), 7.12 (ddd, J = 8.1, 7.4, 1.7 Hz, 1H), 7.07 (dd, J = 7.5, 1.7 Hz, 1H), 6.89 (dd, J = 10.2, 0.7 Hz, 1H), 6.86 (td, J = 7.4, 1.1 Hz, 1H), 6.74 (dt, J = 8.3, 0.9 Hz, 1H), 6.50 (d, J = 8.6 Hz, 1H), 5.68 (d, J = 10.2 Hz, 1H), 2.83 (s, 3H), 2.35 (s, 3H), 2.34 (s, 3H), 1.36 (s, 3H), 1.20 (s, 3H). ESI-MS [M+H] + C 28 H 28 NO2 + Calculated m / z value: 410.211, measured value: 410.222.

[0277]

change

[0278] 1 H NMR (400 MHz, クロロホルム-d) δ 7.45 (dd, J = 8.4, 2.2 Hz, 2H), 7.40 - 7.31 (m, 6H), 6.85 (d, J = 8.5 Hz, 2H), 6.75 (d, J = 8.4 Hz, 2H), 6.48 - 6.42 (m, 2H), 5.85 (d, J = 8.4 Hz, 2H), 2.81 (s, 6H), 1.32 (s, 6H), 1.20 (s, 6H). ESI-MS [M+H] + C 41 H 35 N4O3 + Calculated m / z value: 631.270, measured value: 631.284.

[0279]

change

[0280] 1¹H NMR (500 MHz, salt-mesh-d²) δ 7.72 (dd, J = 8.4, 1.9 Hz, 1H), 7.51 (dd, J = 2.0, 1.0 Hz, 1H), 7.15 - 7.09 (m, 1H), 7.08 (td, J = 7.8, 1.5 Hz, 1H), 6.80 (d, J = 8.5 Hz, 1H), 6.66 - 6.59 (m, 1H), 6.54 (dd, J = 7.9, 1.4 Hz, 1H), 6.46 (dd, J = 8.6, 1.0 Hz, 1H), 5.84 (d, J = 8.6 Hz, 1H), 2.81 (s, 3H), 2.28 (s, 6H), 1.36 (s, 3H), 1.30 - 1.26 (m, 6H), 1.19 (s, 3H). ESI-MS [M+H] + C 25 H 31 N2O2 + のm / z calculated value: 391.238, measured value: 391.230.

[0281]

change

[0282] 1 H NMR (500 MHz, クロロホルム-d) δ 7.80 - 7.73 (m, 2H), 7.69 - 7.62 (m, 1H), 7.49 - 7.39 (m, 3H), 7.26 (dd, J = 2.0, 1.0 Hz, 1H), 7.11 (dd, J = 8.2, 1.7 Hz, 1H), 7.04 (td, J = 7.7, 1.4 Hz, 1H), 6.61 (d, J = 8.4 Hz, 1H), 6.54 - 6.44 (m, 3H), 5.90 (d, J = 8.8 Hz, 1H), 4.11 - 4.00 (m, 2H), 3.58 - 3.49 (m, 2H), 1.35 (s, 3H), 1.25 (s, 3H). ESI-MS [M+H] + C 27 H26 NO3 + Calculated m / z value: 412.508, measured value: 412.499.

[0283]

change

[0284] 1 H NMR (500 MHz, アセトニトリル-d3) δ 7.87 - 7.79 (m, 2H), 7.65 - 7.57 (m, 1H), 7.56 - 7.48 (m, 2H), 7.48 - 7.41 (m, 2H), 7.21 (dd, J = 7.7, 1.5 Hz, 1H), 7.11 - 7.06 (m, 1H), 6.97 (d, J = 8.1 Hz, 1H), 6.88 (td, J = 7.8, 1.6 Hz, 1H), 6.65 (dd, J = 7.8, 1.4 Hz, 1H), 6.54 (dd, J = 8.6, 1.0 Hz, 1H), 5.83 (d, J = 8.5 Hz, 1H), 3.80 - 3.72 (m, 1H), 3.62 - 3.51 (m, 1H), 3.50 - 3.42 (m, 2H), 3.09 (s, 9H), 2.21 - 2.10 (m, 2H), 1.34 (s, 3H), 1.14 (s, 3H). ESI-MS [M] + C 31 H 35 N2O2 + Calculated m / z value: 467.269, measured value: 467.278.

[0285]

change

[0286] 1H NMR (500 MHz, methylene chloride-d2) δ 7.80 - 7.71 (m, 2H), 7.53 - 7.45 (m, 1H), 7.40 - 7.31 (m, 4H), 7.25 (dd, J = 7.8, 1.5 Hz, 1H), 7.17 (dd, J = 7.7, 1.8 Hz, 1H), 7.01 (td, J = 7.7, 1.6 Hz, 1H), 6.77 - 6.67 (m, 2H), 6.60 - 6.58 (m, 1H), 2.99 (s, 3H), 2.31 (d, J = 1.1 Hz, 3H). ESI-MS [M+H] + C 24 H 20 NO2S + Calculated m / z: 386.121, measured: 386.125.

[0287] Synthesis of compounds 10-12 The corresponding acid chloride derivative (15 mmol) and unsubstituted spiropyran (5 mmol) or 8'-methoxyspiropyran (5 mmol) are dissolved in dichloromethane (50 mL) and cooled to 0 °C. AlCl (17 mmol) is added portionwise over 1 h. The resulting mixture is stirred at room temperature for 2 h. The mixture is poured onto ice (200 g) and extracted with dichloromethane. The combined organic layers are dried over anhydrous MgSO, and the solvent is evaporated under reduced pressure. The solid residue is purified by recrystallization from ethanol or by silica gel column chromatography using an acetone / petroleum ether mixture as the eluent.

[0288] [ka]

[0289] 1¹H NMR (500 MHz, salt-mech-d²) δ 7.87 - 7.81 (m, 4H), 7.70 (d, J = 1.9 Hz, 1H), 7.64 - 7.55 (m, 2H), 7.43 - 7.35 (m, 5H), 7.11 - 7.04 (m, 2H), 6.79 (d, J = 8.3 Hz, 1H), 6.44 (dd, J = 8.6, 1.0 Hz, 1H), 6.05 (d, J = 8.5 Hz, 1H), 3.81 (s, 3H), 2.83 (s, 3H), 1.31 (s, 3H), 1.14 (s, 3H). ESI-MS [M+H] + C 34 H 30 NO4 + のm / z calculated value: 516.217, measured value: 516.210.

[0290]

change

[0291] 1 ¹H NMR (500 MHz, salt-mech-d²) δ 7.75 - 7.67 (m, 4H), 7.59 (d, J = 1.8 Hz, 1H), 7.43 - 7.31 (m, 3H), 6.96 - 6.90 (m, 4H), 6.74 (dd, J = 8.5, 5.4 Hz, 2H), 6.34 (dd, J = 8.7, 0.9 Hz, 1H), 5.84 (d, J = 8.6 Hz, 1H), 3.74 (s, 6H), 2.80 (s, 3H), 1.34 (s, 3H), 1.14 (s, 3H). ESI-MS [M+H] + C 35 H 32 NO5 + Calculated m / z value: 546.227, measured value: 546.218.

[0292] Synthesis of compounds 22, 25, 64, and 68 6'-Bromospiropyran (3 mmol) is dissolved in dry tetrahydrofuran (15 mL) and cooled to -78 °C. n-Butyllithium (3.1 mmol) is added dropwise and the solution is stirred for 30 min. The corresponding nitrile derivative (5 mmol) is added over 15 min and the reaction is allowed to warm to room temperature. Stirring is continued at room temperature for 2 h, after which water is added and the reaction mixture is extracted with dichloromethane. The combined organic layers are dried over anhydrous MgSO4 and the solvent is evaporated under reduced pressure. The solid residue is purified by recrystallization from ethanol or by silica gel column chromatography using an acetone / petroleum ether mixture as eluent.

[0293] [ka]

[0294] 1 H NMR (400 MHz, chloroform-d) δ 7.70 (dd, J = 8.6, 2.3 Hz, 1H), 7.64 (d, J = 2.2 Hz, 1H), 7.24 - 7.16 (m, 1H), 7.10 (dd, J = 7.3, 1.3 Hz, 1H), 6.94 - 6.85 (m, 2H), 6.71 (d, J = 8.6 Hz, 1H), 6.56 (d, J = 7.7 Hz, 1H), 5.75 (d, J = 10.3 Hz, 1H), 2.75 (s, 3H), 1.39 (s, 9H), 1.32 (s, 3H), 1.19 (s, 3H). ESI-MS [M+H] + C 24 H 28 NO2 + Calculated m / z: 362.211, measured: 362.219.

[0295] [ka]

[0296] 1H NMR (500 MHz, クロロホルム-d) δ 7.30 - 7.26 (m, 1H), 7.20 (dd, J = 8.3, 1.8 Hz, 1H), 7.15 - 7.09 (m, 2H), 7.00 - 6.94 (m, 1H), 6.75 (d, J = 8.3 Hz, 1H), 6.56 - 6.50 (m, 1H), 6.30 (dd, J = 8.6, 1.0 Hz, 1H), 5.78 (d, J = 8.5 Hz, 1H), 2.99 (s, 3H), 1.30 (s, 3H), 1.25 (s, 6H), 1.14 (s, 3H), 0.12 (s, 9H). ESI-MS [M+H] + C 26 H 34 NO3Si + Calculated m / z value: 436.230, measured value: 436.238.

[0297]

change

[0298] 1 H NMR (500 MHz, クロロホルム-d) δ 7.45 - 7.37 (m, 2H), 7.21 - 7.13 (m, 2H), 6.99 - 6.92 (m, 1H), 6.65 (d, J = 8.3 Hz, 1H), 6.62 - 6.58 (m, 1H), 6.54 (dd, J = 8.6, 1.0 Hz, 1H), 5.80 (d, J = 8.6 Hz, 1H), 2.81 (s, 3H), 2.69 - 2.52 (m, 2H), 1.83 - 1.74 (m, 2H), 1.62 - 1.46 (m, 4H), 1.33 (s, 3H), 1.17 (s, 2H), 0.19 (s, 6H). ESI-MS [M+H] + C 29 H 38 NO3Si + Calculated m / z value: 476.262, measured value: 476.269.

[0299] Synthesis of compounds 23 and 24 2-Mercaptobenzoic acid (0.5 mmol) or phthalic anhydride (0.5 mmol) is slowly dissolved in sulfuric acid (1 mL) and stirred for 15 minutes. 5-Trifluoromethylspiropyran (0.5 mmol) is slowly added over 30 minutes, and stirring is continued for 2 hours. Ice (10 g) is added, and the mixture is neutralized with aqueous Na2CO3 (10%). The reaction mixture is extracted with ethyl acetate. The combined organic layers are dried over anhydrous MgSO4, and the solvent is evaporated under reduced pressure. The residue is purified by silica gel column chromatography using an ethyl acetate / petroleum ether mixture as the eluent.

[0300] [ka]

[0301] 1 H NMR (400 MHz, benzene-d6) δ 8.99 (dd, J = 10.8, 0.7 Hz, 1H), 8.84 - 8.75 (m, 1H), 7.51 (ddd, J = 8.1, 1.9, 0.9 Hz, 1H), 7.47 (d, J = 1.8 Hz, 1H), 7.15 - 7.11 (m, 1H), 7.11 - 7.03 (m, 2H), 6.81 (d, J = 8.7 Hz, 1H), 6.67 - 6.59 (m, 1H), 6.21 (d, J = 8.1 Hz, 1H), 5.57 (d, J = 10.8 Hz, 1H), 2.54 (s, 3H), 1.24 (s, 3H), 0.99 (s, 3H). ESI-MS [M+H] + C 27 H 21 F3NO2S + Calculated m / z: 480.124, measured: 480.116.

[0302] [ka]

[0303] 1 H NMR (500 MHz, chloroform-d) δ 8.06 - 7.98 (m, 3H), 7.91 - 7.84 (m, 2H), 7.64 (s, 1H), 7.34 (d, J = 2.1 Hz, 1H), 7.26 (dd, J = 8.3, 2.2 Hz, 1H), 6.62 (d, J = 8.5 Hz, 1H), 6.34 (dd, J = 8.6, 1.0 Hz, 1H), 5.91 (d, J = 8.6 Hz, 1H), 2.81 (s, 2H), 1.39 (s, 2H), 1.19 (s, 2H). ESI-MS [M+H] + C 28 H 21 F3NO3 + Calculated m / z: 476.147, measured: 476.152.

[0304] Synthesis of compound 26 Compound 25 (3 mmol) is dissolved in tetrahydrofuran and tetrabutylammonium fluoride (1 M in THF, 4.5 mmol) is added. The mixture is stirred for 1 hour and extracted with ethyl acetate. The combined organic layers are washed with water and dried over anhydrous MgSO4. The solvent is evaporated under reduced pressure, and the residue is purified by silica gel column chromatography using an ethyl acetate / petroleum ether mixture as the eluent. The resulting alcohol is dissolved in acetonitrile. Iodomethane (6 mmol) and Cs2CO3 (6 mmol) are added, and the mixture is heated at 70 °C overnight. After cooling to room temperature, water is added, and the mixture is extracted with ethyl acetate. The combined organic layers are dried over anhydrous MgSO4, and the solvent is evaporated under reduced pressure. The residue is purified by silica gel column chromatography using an acetone / petroleum ether mixture as the eluent.

[0305] [ka]

[0306] 1H NMR (400 MHz, chloroform-d) δ 7.48 - 7.44 (m, 1H), 7.41 (dd, J = 8.2, 1.9 Hz, 1H), 7.00 (dd, J = 8.0, 1.0 Hz, 1H), 6.91 (td, J = 7.6, 1.2 Hz, 1H), 6.70 (d, J = 8.3 Hz, 1H), 6.55 - 6.46 (m, 2H), 6.40 (dd, J = 8.8, 1.0 Hz, 1H), 5.78 (d, J = 8.8 Hz, 1H), 3.30 (s, 3H), 2.78 (s, 3H), 1.48 (s, 6H), 1.29 (s, 3H), 1.18 (s, 3H). ESI-MS [M+H] + C 24 H 27 No. 3 + Calculated m / z: 378.206, measured: 378.219.

[0307] Synthesis of compound 27 2-Bromo-2-methylpropionyl bromide (5.25 mmol) is dissolved in dichloromethane (50 mL) and cooled to 0 °C. AlCl (5.5 mmol) is added portionwise and stirring is continued for 15 min. 5-Trifluoromethylspiropyran (5 mmol) is added over 30 min and stirring is continued for 2 h. The reaction is poured onto ice (50 g) and extracted with dichloromethane. The combined organic layers are dried over anhydrous MgSO and the solvent is evaporated under reduced pressure. The residue is purified by silica gel column chromatography using an ethyl acetate / petroleum ether mixture as eluent.

[0308] The resulting α-bromobutyrate (2 mmol) is dissolved in acetonitrile (25 mL) and sodium tolylsulfinate (2.5 mmol) is added. The mixture is heated to reflux for 4 hours. After cooling to room temperature, water is added and the mixture is extracted with ethyl acetate. The combined organic layers are dried over anhydrous MgSO4 and the solvent is evaporated under reduced pressure. The residue is purified by silica gel column chromatography using an acetone / petroleum ether mixture as the eluent.

[0309] [ka]

[0310] 1 H NMR (400 MHz, chloroform-d) δ 7.43 (dd, J = 1.8, 1.1 Hz, 1H), 7.40 - 7.33 (m, 3H), 7.28 - 7.22 (m, 2H), 7.01 (dd, J = 7.8, 1.0 Hz, 1H), 6.89 (td, J = 7.5, 1.0 Hz, 1H), 6.73 (d, J = 8.3 Hz, 1H), 6.46 - 6.35 (m, 3H), 5.74 (d, J = 8.6 Hz, 1H), 2.78 (s, 3H), 2.35 (s, 3H), 1.49 (s, 6H), 1.29 (s, 3H), 1.17 (s, 3H). ESI-MS [M+H] + C 30 H 32 NO4S + Calculated m / z: 502.205, measured: 502.216.

[0311] Synthesis of compound 30 2,2,2-Trichloroacetyl chloride (2.1 mmol) is dissolved in dichloromethane (20 mL) and cooled to 0 °C. AlCl (2.2 mmol) is added portionwise and stirring is continued for 15 min. 5-Trifluoromethylspiropyran (2 mmol) is added over 30 min and stirring is continued for 2 h. The reaction is poured onto ice (20 g) and extracted with dichloromethane. The combined organic layers are dried over anhydrous MgSO and the solvent is evaporated under reduced pressure. The residue is purified by silica gel column chromatography using an ethyl acetate / petroleum ether mixture as eluent.

[0312] [ka]

[0313] 1 H NMR (500 MHz, chloroform-d) δ 7.59 (dd, J = 8.4, 1.7 Hz, 1H), 7.44 (dd, J = 1.9, 1.0 Hz, 1H), 7.34 (d, J = 2.1 Hz, 1H), 7.19 (dd, J = 8.3, 2.1 Hz, 1H), 6.69 (d, J = 8.4 Hz, 1H), 6.60 (d, J = 8.5 Hz, 1H), 6.37 (dd, J = 8.6, 1.0 Hz, 1H), 5.86 (d, J = 8.5 Hz, 1H), 2.80 (s, 3H), 1.21 (s, 3H), 1.09 (s, 3H). ESI-MS [M+H] + C 22 H 18 Cl3F3NO2 + Calculated m / z: 490.035, measured: 490.180.

[0314] Synthesis of compounds 58-60 and 63 5-Trifluoromethylspiropyran (5 mmol), MgCl2 (7.5 mmol), triethylamine (18.75 mmol), and paraformaldehyde (33.75 mmol) are dissolved in THF and heated at 70 °C for 3 days. The mixture is cooled to room temperature, neutralized with 1 M aqueous HCl, and extracted with ethyl acetate. The combined organic layers are dried over anhydrous MgSO4, and the solvent is evaporated under reduced pressure. The residue is purified by silica gel column chromatography using an ethyl acetate / petroleum ether mixture as the eluent. The reaction is carried out similarly using 5-trifluoromethyl-5',7'-dimethylspiropyran, 5-trifluoromethyl-5',7'-dimethoxyspiropyran, or 5-trifluoromethyl-6',7'-difluoro-N-(3,5-dimethylbenzyl)-spiropyran.

[0315] 5-Trifluoromethyl-6'-formylspiropyran (2.5 mmol) and diphenylphosphine oxide (2.5 mmol) are dissolved in THF (25 mL) under an argon atmosphere. Triethylamine (2.5 mmol) is added dropwise, and stirring is continued for 18 hours. Water is added, and the mixture is extracted with ethyl acetate. The combined organic layers are dried over anhydrous MgSO4, and the solvent is evaporated under reduced pressure. The residue is purified by silica gel column chromatography using an ethyl acetate / petroleum ether mixture as the eluent. The reaction is carried out similarly with 5-trifluoromethyl-5',7'-dimethyl-6'-formylspiropyran, 5-trifluoromethyl-5',7'-dimethoxy-6'-formylspiropyran, or 5-trifluoromethyl-6',7'-difluoro-N-(3,5-dimethyl-4-formylbenzyl)-spiropyran.

[0316] The corresponding formylspiropyran derivative (1.5 mmol) and MnO2 (30 mmol) are mixed in dichloromethane and stirred overnight. The reaction is filtered through Celite and the solvent is evaporated under reduced pressure. The desired product is obtained by silica gel column chromatography using ethyl acetate / petroleum ether mixture as eluent.

[0317] [ka]

[0318] 1H NMR (400 MHz, クロロホルム-d) δ 8.47 (d, J = 2.2 Hz, 1H), 8.32 (dd, J = 8.7, 2.2 Hz, 1H), 7.92 - 7.83 (m, 5H), 7.56 (td, J = 7.3, 1.5 Hz, 2H), 7.48 (tdd, J = 10.3, 7.5, 4.8 Hz, 6H), 6.98 (d, J = 10.4 Hz, 1H), 6.81 - 6.75 (m, 1H), 6.54 (d, J = 8.2 Hz, 1H), 5.74 (d, J = 10.4 Hz, 1H), 2.75 (s, 3H), 1.28 (s, 3H), 1.17 (s, 3H). ESI-MS [M+H] + C 33 H 28 F3NO3P + Calculated m / z value: 574.175, measured value: 574.189.

[0319]

change

[0320] 1 H NMR (400 MHz, クロロホルム-d) δ 8.01 - 7.94 (m, 4H), 7.61 - 7.52 (m, 2H), 7.44 - 7.32 (m, 5H), 7.28 (dd, J = 8.3, 1.8 Hz, 1H), 6.75 - 6.63 (m, 2H), 6.55 (d, J = 8.7 Hz, 1H), 5.80 (d, J = 8.5 Hz, 1H), 2.87 (s, 3H), 2.44 (s, 6H), 1.31 (s, 3H), 1.11 (s, 3H). ESI-MS [M+H] + C 35 H 32 F3NO3P + のm / z calculated value: 602.207, measured value: 602.199.

[0321]

change

[0322] 1 H NMR (400 MHz, クロロホルム-d) δ 8.01 - 7.95 (m, 4H), 7.58 - 7.50 (m, 2H), 7.42 - 7.35 (m, 5H), 7.31 (dd, J = 8.4, 1.7 Hz, 1H), 6.80 (d, J = 8.3 Hz, 1H), 6.74 (d, J = 8.9 Hz, 1H), 6.44 (s, 1H), 5.82 (d, J = 8.8 Hz, 1H), 3.84 (s, 6H), 2.87 (s, 3H), 1.29 (s, 3H), 1.14 (s, 3H). ESI-MS [M+H] + C 35 H 32 F3NO5P + Calculated m / z value: 634.196, measured value: 634.182.

[0323]

change

[0324] 1H NMR (400 MHz, chloroform-d) δ 7.87 - 7.81 (m, 4H), 7.54 - 7.47 (m, 2H), 7.42 - 7.34 (m, 5H), 7.30 - 7.20 (m, 1H), 7.18 (ddd, J = 7.9, 4.9, 1.0 Hz, 1H), 7.15 (t, J = 1.0 Hz, 2H), 6.89 (d, J = 8.3 Hz, 1H), 6.62 (dd, J = 8.0, 5.0 Hz, 1H), 6.53 (dd, J = 8.7, 0.9 Hz, 1H), 5.82 (d, J = 8.5Hz, 1H), 4.80 (dt, J = 13.0, 1.0 Hz, 1H), 4.41 (dt, J = 13.0, 1.0 Hz, 1H), 2.41 (s, 6H), 1.34 (s, 2H), 1.23 (s, 2H). ESI-MS [M+H] + C 41 H 34 F5NO3P + Calculated m / z: 714.219, measured: 714.211.

[0325] Synthesis of compound 61 5-Trifluoromethyl-6'-formylspiropyran (5 mmol) and 1,3-propanedithiol (5 mmol) are dissolved in chloroform (10 mL) and cooled to -10 °C. Gaseous HCl is passed through the solution for 45 min, and stirring is continued at 0 °C for 30 min and at room temperature overnight. The solvent is evaporated under reduced pressure, and the residue is suspended in methanol (5 mL). The slurry is stirred overnight and filtered. The solid residue is dried under reduced pressure.

[0326] The dithiane derivative (5 mmol) is dissolved in dry tetrahydrofuran (10 mL) under an argon atmosphere and cooled to -78 °C. n-Butyllithium (1.6 M in hexane, 5 mmol) is added dropwise. The solution is warmed to 0 °C and stirred for 30 minutes. Diethylgermanium dichloride (2 mmol) in dry tetrahydrofuran (5 mL) is added dropwise and stirred at 0 °C for 3 hours and at room temperature overnight. Water is added and the mixture is extracted with ethyl acetate. The combined organic layers are washed with water and dried over anhydrous MgSO4. The solvent is removed under reduced pressure. Ethyl acetate (2.5 mL) is added to the solid residue to obtain a suspension. After stirring overnight, methanol (5 mL) is added and stirring is continued for 24 hours. The suspension is filtered, washed with ethyl acetate / methanol (1 / 1) and dried under reduced pressure.

[0327] The dithianediethylgermanium derivative (1.5 mmol) is dissolved in tetrahydrofuran (10 mL) and water (2 mL) is added. CaCO3 (1.8 mmol) and iodine (1.8 mmol) are added portionwise over 4 hours with intermittent ice cooling. The reaction mixture is stirred overnight at room temperature and filtered through silica gel. A saturated aqueous solution of sodium dithionite is added until the color of the resulting suspension changes to yellow. The mixture is filtered and washed with water. The residue is dissolved in ethyl acetate and washed with water. The organic phase is dried over anhydrous MgSO4 and the solvent is evaporated under reduced pressure. Silica gel column chromatography using ethyl acetate / petroleum ether as eluent gives the desired product.

[0328] [ka]

[0329] 1H NMR (500 MHz, chloroform-d) δ 8.15 - 8.03 (m, 4H), 7.51 (dd, J = 8.4, 2.1 Hz, 2H), 7.45 (d, J = 2.0 Hz, 2H), 7.32 (d, J = 8.4 Hz, 2H), 7.12 (d, J = 8.2 Hz, 2H), 6.48 - 6.42 (m, 2H), 5.80 (d, J = 8.7 Hz, 2H), 2.75 (s, 6H), 2.08 (q, J = 6.7 Hz, 4H), 1.39 (s, 6H), 1.33 (t, J = 6.8 Hz, 6H), 1.19 (s, 6H). ESI-MS [M+H] + C 46 H 45 F6GeN2O4 + Calculated m / z: 877.249, measured: 877.221.

[0330] Synthesis of compound 65 2-Bromo-2-methylpropionyl bromide (5.25 mmol) is dissolved in dichloromethane (50 mL) and cooled to 0 °C. AlCl (5.5 mmol) is added portionwise and stirring is continued for 15 min. 5-Trifluoromethylspiropyran (5 mmol) is added over 30 min and stirring is continued for 2 h. The reaction is poured onto ice (50 g) and extracted with dichloromethane. The combined organic layers are dried over anhydrous MgSO and the solvent is evaporated under reduced pressure. The residue is purified by silica gel column chromatography using an ethyl acetate / petroleum ether mixture as eluent.

[0331] The resulting α-bromobutyrate (2 mmol) is dissolved in morpholine (10 mL) and heated at 80° C. for 2 days. After cooling to room temperature, water is added and the mixture is extracted with ethyl acetate. The combined organic layers are dried over anhydrous MgSO4 and the solvent is evaporated under reduced pressure. The residue is purified by silica gel column chromatography using an acetone / petroleum ether mixture as the eluent.

[0332] Alternatively, the obtained α-bromobutyrate (2 mmol) is dissolved in toluene (2 mL) and added dropwise to a methanolic solution of sodium methylate (30%, 10 mL) at 0°C and stirred for 8 hours. The suspension is filtered, morpholine (20 mL) is added to the solid residue, and the mixture is heated at 130°C for 24 hours. After cooling to room temperature, water is added and the mixture is extracted with ethyl acetate. The combined organic layers are dried over anhydrous MgSO4, and the solvent is evaporated under reduced pressure. The residue is purified by silica gel column chromatography using an acetone / petroleum ether mixture as the eluent.

[0333] [ka]

[0334] 1 H NMR (400 MHz, chloroform-d) δ 7.50 (dd, J = 8.4, 1.9 Hz, 1H), 7.48 - 7.41 (m, 2H), 7.37 (dd, J = 8.4, 1.9 Hz, 1H), 6.85 (d, 8.4 Hz, 1H), 6.83 (d, 8.4 Hz, 1H), 6.52 (dd, J = 8.6, 1.0 Hz, 1H), 5.84 (d, J = 8.6 Hz, 1H), 3.72 - 3.65 (m, 2H), 3.64 - 3.58 (m, 2H), 2.88 (s, 3H), 2.70 - 2.63 (m, 4H), 1.35 (s, 3H), 1.30 (s, 6H), 1.19 (s, 3H). ESI-MS [M+H] + C 28 H 32 F3N2O3 + Calculated m / z: 501.236, measured: 501.240.

[0335] Synthesis of compounds 66 and 67 2-Bromobutyryl bromide (5.25 mmol) is dissolved in dichloromethane (50 mL) and cooled to 0 °C. AlCl (5.5 mmol) is added portionwise and stirring is continued for 15 min. 5-Trifluoromethylspiropyran (5 mmol) is added over 30 min and stirring is continued for 2 h. The reaction is poured onto ice (50 g) and extracted with dichloromethane. The combined organic layers are dried over anhydrous MgSO and the solvent is evaporated under reduced pressure. The residue is purified by silica gel column chromatography using an ethyl acetate / petroleum ether mixture as eluent.

[0336] The resulting α-bromobutyrate (2 mmol) is dissolved in tetrahydrofuran and added dropwise to a solution of the corresponding amine in tetrahydrofuran (2 M, 10 mmol) at 0° C. The mixture is stirred at 0° C. for 2 h and then at room temperature for a further 4 h. The solvent is evaporated under reduced pressure to give the α-aminobutyrate, which is used directly in the next step.

[0337] The resulting α-aminobutyrate (2 mmol) is dissolved in acetonitrile (10 mL) and benzyl bromide (2.5 mmol) and heated at 70°C for 2 hours. After cooling to room temperature, the solvent is evaporated under reduced pressure and the remaining crude product is suspended in ethanol (10 mL). Aqueous NaOH (30%, 10 mL) is added and the mixture is heated at 60°C for 4 hours. After cooling to room temperature, the mixture is neutralized with 1 M aqueous HCl and extracted with ethyl acetate. The combined organic layers are dried over anhydrous MgSO4 and the solvent is evaporated under reduced pressure. The residue is purified by silica gel column chromatography using an acetone / petroleum ether mixture as the eluent.

[0338] [ka]

[0339] 1H NMR (500 MHz, クロロホルム-d) δ 7.65 - 7.56 (m, 2H), 7.44 (d, J = 1.8 Hz, 1H), 7.38 - 7.28 (m, 3H), 7.27 - 7.15 (m, 3H), 6.82 (dd, J = 8.3, 0.9 Hz, 2H), 6.54 (dd, J = 8.6, 1.0 Hz, 1H), 5.81 (d, J = 8.6 Hz, 1H), 3.50 (t, J = 1.0 Hz, 2H), 2.82 (s, 3H), 2.42 (s, 6H), 1.98 -1.88 (m, 2H), 1.35 (s, 3H), 1.19 (s, 2H), 0.91 (t, J = 7.2 Hz, 3H). ESI-MS [M+H] + C 33 H 36 F3N2O2 + Calculated m / z value: 549.272, measured value: 549.284.

[0340]

change

[0341] 1 H NMR (400 MHz, クロロホルム-d) δ 7.56 (d, J = 1.8 Hz, 1H), 7.44 - 7.38 (m, 2H), 7.37 - 7.28 (m, 2H), 7.31 - 7.21 (m, 4H), 6.65 (dd, J = 8.5, 0.9 Hz, 2H), 6.35 (dd, J = 8.6, 1.0 Hz, 1H), 5.81 (d, J = 8.5 Hz, 1H), 3.61 (t, J = 5.9 Hz, 4H), 3.51 (t, J = 0.9 Hz, 2H), 2.84 (s, 3H), 3.06 - 2.93 (m, 3H), 2.44 - 2.38 (m, 2H), 1.93 - 1.82 (m, 2H), 1.32 (s, 3H), 1.20 (s, 3H), 0.96 (t, J = 7.1 Hz, 3H). ESI-MS [M+H] + C 35 H 38 F3N2O3 + Calculated m / z: 591.283, measured: 591.288.

[0342] Synthesis of compound 69 Compound 68 (3 mmol) is dissolved in tetrahydrofuran and tetrabutylammonium fluoride (1 M in THF, 4.5 mmol) is added. The mixture is stirred for 1 hour and extracted with ethyl acetate. The combined organic layers are washed with water and dried over anhydrous MgSO. The solvent is evaporated under reduced pressure and the residue is purified by silica gel column chromatography using an ethyl acetate / petroleum ether mixture as the eluent.

[0343] [ka]

[0344] 1 H NMR (400 MHz, chloroform-d) δ 7.95 (dd, J = 8.7, 2.2 Hz, 1H), 7.90 (d, J = 2.2 Hz, 1H), 7.20 (td, J = 7.7, 1.2 Hz, 1H), 7.09 (d, J = 7.1 Hz, 1H), 6.92 (d, J = 10.3 Hz, 1H), 6.87 (t, J = 7.4 Hz, 1H), 6.73 (d, J = 8.6 Hz, 1H), 6.55 (d, J = 7.8 Hz, 1H), 5.76 (d, J = 10.3 Hz, 1H), 3.54 (s, 1H), 2.74 (s, 3H), 2.13 - 1.98 (m, 2H), 1.89 - 1.63 (m, 8H), 1.30 (s, 3H), 1.18 (s, 3H). ESI-MS [M+H] + C 26 H 30 No. 3 + Calculated m / z: 404.222, measured: 404.228.

[0345] Synthesis of compounds 71-74 Compound 70 (2 mmol) is dissolved in dry dichloromethane (5 mL) and the corresponding isocyanate is added dropwise. The reaction mixture is stirred for 1 hour, and the solvent is removed under reduced pressure. The residue is purified by silica gel column chromatography using acetone / petroleum ether or methanol / dichloromethane mixtures as the eluent.

[0346] [ka]

[0347] 1 H NMR (500 MHz, chloroform-d) δ 7.87 - 7.80 (m, 2H), 7.65 - 7.64 (m, 2H), 7.48 - 7.40 (m, 3H), 7.5 - 7.05 (m, 2H), 7.04 (ddd, J = 7.9, 7.2, 1.9 Hz, 1H), 6.76 (d, J = 8.4 Hz, 1H), 6.55 (dd, J = 7.9, 1.4 Hz, 1H), 6.28 (dd, J = 8.6, 1.0 Hz, 1H), 6.18 - 6.14 (m, 1H), 5.93 - 5.82 (m, 2H), 5.36 (t, J = 4.2 Hz, 1H), 4.52 - 4.44 (m, 1H), 4.32 - 4.22 (m, 3H), 3.91 - 3.82 (m, 1H), 3.78 - 3.69 (m, 1H), 3.69 - 3.60 (m, 1H), 3.31 - 3.21 (m, 1H), 1.93 (t, J = 0.9 Hz, 3H), 1.29 (s, 3H), 1.15 (s, 3H). ESI-MS [M+H] + C 34 H 35 N2O6 + Calculated m / z: 567.249, measured: 567.241.

[0348] [ka]

[0349] 1 H NMR (500 MHz, クロロホルム-d) δ 7.71 - 7.64 (m, 2H), 7.49 - 7.42 (m, 1H), 7.39 - 7.28 (m, 4H), 7.14 - 7.04 (m, 2H), 7.00 (ddd, J = 7.9, 7.1, 1.9 Hz, 1H), 6.70 (d, J = 8.3 Hz, 1H), 6.52 (dd, J = 8.0, 1.4 Hz, 1H), 6.31 (dd, J = 8.7, 1.0 Hz, 1H), 6.08 (dd, J = 10.1, 9.4 Hz, 1H), 5.94 (d, J = 8.8 Hz, 1H), 5.78 (d, J = 9.9 Hz, 2H), 5.53 (t, J = 4.4 Hz, 1H), 4.58 - 4.48 (m, 2H), 4.47 - 4.38 (m, 1H), 4.33 - 4.26 (m, 1H), 3.82 - 3.73 (m, 1H), 3.71 - 3.62 (m, 1H), 3.60 - 3.50 (m, 2H), 1.29 (s, 3H), 1.21 (s, 3H). ESI-MS [M+H] + C 33 H 33 N2O6 + Calculated m / z value: 553.233, measured value: 553.245.

[0350]

change

[0351] 1H NMR (500 MHz, クロロホルム-d) δ 7.98 (d, J = 2.3 Hz, 2H), 7.77 (s, 2H), 7.60 (s, 2H), 7.40 - 7.36 (m, 2H), 7.30 - 7.11 (m, 20H), 7.03 - 6.92 (m, 4H), 6.67 (dd, J = 8.4, 2.1 Hz, 2H), 6.50 (d, J = 8.3 Hz, 2H), 6.29 (dd, J = 8.6, 0.9 Hz, 2H), 5.62 - 5.56 (m, 2H), 5.03 - 4.97 (m, 2H), 4.54 - 4.42 (m, 4H), 4.02 - 3.91 (m, 4H), 3.85 - 3.74 (m, 32H), 3.56 - 3.42 (m, 64H), 3.42 - 3.35 (m, 4H), 2.30 (s, 6H), 1.39 (d, J = 6.4 Hz, 6H), 1.32 - 1.24 (m, 96H), 1.24 (s, 6H), 1.14 (s, 6H). ESI-MS [M+2H] 2+ C 174 H 270 N6O 45 2+ のm / z calculated value: 1582.452, measured value: 1582.436.

[0352]

change

[0353] 1H NMR (500 MHz, chloroform-d) δ 7.85 - 7.79 (m, 2H), 7.54 - 7.44 (m, 2H), 7.44 - 7.35 (m, 3H), 7.16 - 7.07 (m, 2H), 7.06 - 7.01 (m, 1H), 6.99 - 6.92 (m, 2H), 6.47 (dd, J = 8.6, 1.0 Hz, 1H), 5.83 (d, J = 8.5 Hz, 1H), 5.56 (t, J = 4.4 Hz, 1H), 4.54 (d, J = 3.1 Hz, 2H), 4.30 - 4.19 (m, 2H), 3.83 - 3.72 (m, 2H), 3.71 - 3.55 (m, 440H), 3.43 - 3.30 (m, 2H), 3.25 (s, 3H), 1.27 (s, 3H), 1.19 (s, 3H).

[0354] Synthesis of compounds 75 and 76 Compound 70 (3 mmol) is dissolved in acetonitrile (25 mL) and cooled to 0 °C. Tosyl chloride (10 mmol) or 2-bromomethyl-1,4-benzodioxane (10 mmol) and K2CO3 (11 mmol) are added, and the mixture is heated at 70 °C for 2 days. The reaction mixture is stirred for 1 hour, and the solvent is removed under reduced pressure. The residue is purified by silica gel column chromatography using acetone / petroleum ether mixtures or methanol / dichloromethane mixtures as eluents. Water is added, and the mixture is extracted with ethyl acetate. The combined organic layers are dried over anhydrous MgSO4, and the solvent is evaporated under reduced pressure. The residue is purified by silica gel column chromatography using acetone / petroleum ether mixtures as eluents.

[0355] [ka]

[0356] 1H NMR (500 MHz, クロロホルム-d) δ 7.71 - 7.64 (m, 2H), 7.61 - 7.50 (m, 2H), 7.49 - 7.41 (m, 3H), 7.12 - 7.02 (m, 2H), 7.01 (td, J = 7.5, 1.5 Hz, 1H), 6.97 - 6.79 (m, 5H), 6.66 (dd, J = 7.7, 1.6 Hz, 1H), 6.32 (dd, J = 8.7, 1.1 Hz, 1H), 5.84 (d, J = 8.6 Hz, 1H), 5.54 (t, J = 4.8 Hz, 1H), 4.31 (dd, J = 12.3, 4.9 Hz, 1H), 4.11 (dd, J = 12.1, 4.9 Hz, 1H), 3.89 - 3.76 (m, 2H), 3.75 - 3.67 (m, 1H), 3.51 - 3.45 (m, 1H), 1.31 (s, 3H), 1.16 (s, 3H). ESI-MS [M+H] + C 35 H 32 NO5 + のm / z calculated value: 546.227, measured value: 546.239.

[0357]

change

[0358] 1H NMR (500 MHz, chloroform-d) δ 7.87 - 7.80 (m, 2H), 7.69 - 7.63 (m, 2H), 7.58 - 7.50 (m, 2H), 7.51 - 7.42 (m, 5H), 7.20 (dd, J = 7.7, 1.5 Hz, 1H), 7.04 (td, J = 7.5, 1.3 Hz, 1H), 6.99 (td, J = 7.3, 1.5 Hz, 1H), 6.80 (d, J = 8.4 Hz, 1H), 6.59 (dd, J = 7.8, 1.4 Hz, 1H), 6.39 (dd, J = 8.6, 0.9 Hz, 1H), 5.84 (d, J = 8.8 Hz, 1H), 4.50 - 4.44 (m, 1H), 4.41 - 4.35 (m, 1H), 4.10 - 3.99 (m, 1H), 3.78 - 3.68 (m, 1H), 2.40 (s, 3H), 1.29 (s, 3H), 1.10 (s, 3H). ESI-MS [M+H] + C 34 H 32 NO5S + Calculated m / z: 566.200, measured: 566.208.

[0359] Synthesis of compounds 79 and 80 4-Hydroxybenzophenone (4 mmol), the corresponding 1,1-diaryl-2-propyn-1-ol (4 mmol), and β-cyclodextrin hydrate (320 mg) are dissolved in water (10 mL) and heated at 90 °C overnight. The mixture is extracted with ethyl acetate. The combined organic layers are dried over anhydrous MgSO4, and the solvent is evaporated under reduced pressure. The residue is purified by silica gel column chromatography using an acetone / petroleum ether mixture as the eluent.

[0360] [ka]

[0361] 1H NMR (500 MHz, クロロホルム-d) δ 7.79 - 7.71 (m, 2H), 7.64 (dd, J = 8.4, 2.2 Hz, 1H), 7.58 - 7.54 (m, 2H), 7.51 - 7.43 (m, 2H), 7.37 - 7.31 (m, 4H), 6.95 (dd, J = 8.4, 0.7 Hz, 1H), 6.90 - 6.85 (m, 4H), 6.62 (dd, J = 10.0, 0.7 Hz, 1H), 6.17 (d, J = 9.9 Hz, 1H), 3.80 (s, 6H). ESI-MS [M+H] + C 30 H 25 O4 + Calculated m / z value: 449.175, measured value: 449.184.

[0362]

change

[0363] 1 H NMR (500 MHz, クロロホルム-d) δ 9.49 (d, J = 8.0 Hz, 1H), 9.33 (d, J = 8.2 Hz, 1H), 7.42 - 7.30 (m, 4H), 7.28 (d, J = 4.1 Hz, 3H), 7.24 - 7.17 (m, 4H), 7.12 (d, J = 8.7 Hz, 1H), 6.83 (d, J = 8.8 Hz, 1H), 6.75 (d, J = 9.0 Hz, 2H), 6.48 (d, J = 8.1 Hz, 1H), 6.38 (d, J = 7.9 Hz, 1H), 3.83 - 3.71 (m, 4H), 3.21 - 3.12 (m, 4H). ESI-MS [M+H] + C 32 H 28 NO3 + Calculated m / z value: 474.206, measured value: 474.220.

[0364] Synthesis of anterior body

[0365] [ka]

[0366] 1-Hydroxy-1-carbonitrilecyclohexane (10 g) was dissolved in THF (50 mL) and cooled to -20 °C, then EtN (13 mL) was added. A solution of trimethylsilyl chloride (12 g in 20 mL of THF) was added dropwise. The solution was stirred at -20 °C for 1.5 hours and at room temperature overnight. The mixture was extracted with methyl tert-butyl ether, and the combined organic layers were dried over anhydrous MgSO. The solvent was evaporated under reduced pressure, and the product was obtained after distillation as a clear liquid. 1 H NMR (500 MHz, chloroform-d) δ 1.92 (dt, J = 13.3, 3.3 Hz, 2H), 1.63 (dt, J = 13.2, 3.8 Hz, 2H), 1.55–1.38 (m, 5H), 1.18–1.06 (m, 1H), 0.11 (s, 3H).

[0367] [ka]

[0368] 2-Hydroxy-2-carbonitrilepropane (25 g) was dissolved in THF (150 mL) and cooled to -20 °C, then EtN (46 mL) was added. A solution of trimethylsilyl chloride (42 g in 65 mL of THF) was added dropwise. The solution was stirred at -20 °C for 1.5 hours and at room temperature overnight. The mixture was extracted with methyl tert-butyl ether, and the combined organic layers were dried over anhydrous MgSO. The solvent was evaporated under reduced pressure, and the product was obtained after distillation as a clear liquid. 1 H NMR (500 MHz, chloroform-d) δ 1.58 (s, 6H), 0.22 (s, 9H).

[0369] A general synthesis of salicylaldehyde. The corresponding phenol derivative (5 mmol) and NaOH (105 mmol) are dissolved in water (55 mL) and heated to 70-90 °C. Chloroform (75 mmol) is added and heating is continued until the starting material is consumed. If the reaction stops before completion, additional chloroform (75 mmol) is added. After cooling to room temperature, the mixture is acidified with aqueous hydrochloric acid (10%) and extracted with methyl tert-butyl ether. The combined organic layers are mixed with water (100 mL) and KOH (7.5 g). The aqueous layer is washed with chloroform and then acidified with aqueous hydrochloric acid (10%). The aqueous phase is extracted with methyl tert-butyl ether, and the combined organic extracts from the last step are dried over anhydrous MgSO4. The solvent is removed under reduced pressure, and the resulting product is used directly in the next step without further purification.

[0370] Synthesis of ortho-nitrosophenols The corresponding phenol (25 mmol) is dissolved in acetic acid (150 mL) and NaNO2 (75 mmol) in water (17 mL) is added dropwise at 0 °C. The mixture is stirred at 0 °C for 2 h and then at room temperature for an additional 4 h. Water is added to precipitate the crude product, which is filtered and used without further purification.

[0371] A general synthesis of indolenium salts. The corresponding aniline derivative (50 mmol) is dissolved in a mixture of concentrated aqueous hydrochloric acid (20 mL) and ice water (30 mL). Aqueous NaNO (100 mmol) is added at 0 °C. After stirring for 30 min, SnCl (28.4 g) in concentrated aqueous hydrochloric acid (35 mL) is added. The resulting mixture is stirred for 30 min, filtered, and washed with water or 1 M aqueous hydrochloric acid to give hydrazine hydrochloride, which is used directly in the next step.

[0372] The corresponding hydrazine (as hydrochloride) (47.5 mmol), 3-methylbutan-2-one, and concentrated aqueous sulfuric acid are dissolved in glacial acetic acid (68 mL). The mixture is refluxed for 24 hours, after which the main fraction of acetic acid is distilled off. After cooling to room temperature, the residue is neutralized with saturated aqueous NaHCO3. The mixture is extracted with dichloromethane, and the combined organic phases are dried over anhydrous MgSO4, after which the solvent is evaporated under reduced pressure. If the indole is not pure enough for the next step, silica gel column chromatography is performed using a petroleum ether / ethyl acetate mixture as the eluent.

[0373] The resulting indole (30 mmol) is dissolved in acetonitrile (150 mL) and the corresponding alkyl halide (60 mmol) is added. The mixture is refluxed for 24 hours. After cooling to room temperature, the product precipitates, which is filtered and washed with acetonitrile. If the product does not precipitate, the solvent is evaporated under reduced pressure. The indole is purified by recrystallization from acetonitrile or acetone.

[0374] [ka]

[0375] 1 H NMR (500 MHz, DMSO-d6) δ 7.43 (s, 1H), 7.24 (m, 2H), 4.03 (m, 6H), 0.85 (s, 6H). ESI-MS [M] + C 13 H 15 N2 + Calculated m / z: 199.123, measured: 199.129.

[0376] [ka]

[0377] 1H NMR (500 MHz, アセトニトリル-d3) δ 9.15 (dd, J = 2.2, 0.5 Hz, 1H), 9.05 (dd, J = 8.8, 2.2 Hz, 1H), 8.50 (d, J = 8.8 Hz, 1H), 4.56 (q, J = 0.9 Hz, 3H), 3.37 (q, J = 0.9 Hz, 3H), 2.20 (s, 6H). ESI-MS [M] + C 12 H 15 N2O2 + のm / z calculated value: 219.113, measured value: 219.119.

[0378]

change

[0379] 1 H NMR (500 MHz, DMSO-d6) δ 7.35 (dd, J = 1.6, 0.7 Hz, 1H), 7.24 - 7.15 (m, 2H), 7.04 - 6.97 (m, 2H), 6.94 - 6.85 (m, 1H), 6.82 - 6.73 (m, 2H), 4.04 (s, 3H), 3.31 (s, 3H), 0.85 (s, 6H). ESI-MS [M] + C 19 H 20 NO + のm / z calculated value: 278.154, measured value: 278.158.

[0380]

change

[0381] 1H NMR (500 MHz, DMSO-d6) δ 7.33 (dd, J = 1.7, 0.7 Hz, 1H), 7.22 - 7.14 (m, 2H), 7.06 - 6.99 (m, 2H), 6.78 - 6.69 (m, 1H), 6.57 - 6.48 (m, 2H), 4.04 (s, 3H), 3.31 (s, 3H), 0.85 (s, 6H). ESI-MS [M] + C 19 H 19 FNO + Calculated m / z value: 296.145, measured value: 296.155.

[0382]

change

[0383] 1 H NMR (500 MHz, クロロホルム-d) δ 7.91 (dd, J = 1.6, 0.6 Hz, 1H), 7.88 (dd, J = 8.3, 1.5 Hz, 1H), 7.83 (dd, J = 8.2, 0.6 Hz, 1H), 7.55 (dd, J = 2.0, 0.9 Hz, 1H), 7.46 (dd, J = 7.8, 1.9 Hz, 1H), 7.25 - 7.21 (m, 1H), 4.30 (d, J = 1.0 Hz, 3H), 3.14 (d, J = 1.0 Hz, 3H), 2.32 (d, J = 14.8 Hz, 6H), 1.98 (s, 2H), 1.69 (s, 6H). ESI-MS [M] + C 21 H 24 NO + のm / z calculated value: 306.185, measured value: 306.181.

[0384] Let's start the synthesis together Example 1 Bisphenol A diglycidyl ether (10 g, 29.4 mmol) is added to triethanolamine (26.3 g, 176 mmol) and the mixture is stirred overnight at room temperature. The mixture is dissolved in acetone / methanol (25 / 1) and filtered through silica gel. The solvent is removed under reduced pressure to give the product as a viscous oil. Other amines, such as morpholine, dicyclohexylamine, or dimethylamine, can be used instead of triethanolamine.

[0385] Example 2 2-Isocyanatoethyl acrylate (1 g, 7.1 mmol) is added dropwise to a solution of N-butyl-diethanolamine (3.3 g, 28.4 mmol) in dichloromethane (1 mL) at 0 °C. After stirring at room temperature for 1 h, dichloromethane is added and the mixture is washed with water. After evaporating the solvent under reduced pressure, the product is obtained as a viscous oil. This procedure can be applied to other ethanolamine derivatives and 2-isocyanatoethyl methacrylate.

[0386] Exemplary formulation compositions: Formulation example 1 Initiator 2 (2 mg) was dissolved in ethyl acetate (0.5 g) and added to a mixture of triethanolamine (1 g) and pentaerythritol tetraacrylate (10 g). Add The mixture can be stirred until homogenized and used directly for printing. can .

[0387] Formulation example 2 Initiator 2 (2 mg) was dissolved in ethyl acetate (0.5 g) and added to a mixture of triethanolamine (1 g) and diurethane dimethacrylate, mixture of isomers, CAS 72869-86-4 (10 g). do The mixture can be stirred until homogenized and used directly for printing. can .

[0388] Formulation example 3 Initiator 2 (2 mg) was dissolved in ethyl acetate (0.5 g) and added to a mixture of triethanolamine (1 g), bisphenol A glycerolate (1 glycerol / phenol) diacrylate (5 g), and pentaerythritol tetraacrylate (5 g). do The mixture can be stirred until homogenized and used directly for printing. can .

[0389] Formulation example 4 Initiator 2 (2 mg) was dissolved in ethyl acetate (0.5 g) and added to a mixture of triethanolamine (0.25 g), triethylamine (0.75 g), and pentaerythritol tetraacrylate (10 g). Add The mixture can be stirred until homogenized and used directly for printing. can .

[0390] Formulation example 5 Initiator 2 (2 mg) was dissolved in ethyl acetate (0.5 g) and added to a mixture of triethanolamine (0.75 g), acetic acid (0.25 g), and pentaerythritol tetraacrylate (10 g). Add The mixture can be stirred until homogenized and used directly for printing. can .

[0391] Formulation example 6 Initiator 65 (100 mg) and 2-isopropylthioxanthone (100 mg) were dissolved in ethyl acetate (2 g) and added to pentaerythritol tetraacrylate (10 g). do The mixture can be stirred until homogenized and used directly for printing. can .

[0392] Formulation example 7 Initiator 66 (100 mg) and 2-isopropylthioxanthone (100 mg) were dissolved in ethyl acetate (2 g) and added to pentaerythritol tetraacrylate (10 g). do The mixture can be stirred until homogenized and used directly for printing. can .

[0393] Formulation example 8 Initiator 28 (100 mg) and 2-isopropylthioxanthone (100 mg) were dissolved in ethyl acetate (2 g) and added to pentaerythritol tetraacrylate (10 g). do The mixture can be stirred until homogenized and used directly for printing. can .

[0394] Formulation example 9 Initiator 2 (2 mg) was dissolved in ethyl acetate (0.5 g) and added to a mixture of viscous coinitiator (Example 2, 1 g) and diurethane dimethacrylate, mixture of isomers, CAS 72869-86-4 (10 g). do The mixture can be stirred until homogenized and used directly for printing. can .

[0395] Formulation example 10 Initiator 65 (2 mg) was dissolved in ethyl acetate (0.5 g) and added to pentaerythritol tetraacrylate (10 g). do The mixture can be stirred until homogenized and used directly for printing. can .

[0396] Formulation example 11 Initiator 66 (2 mg) was dissolved in isobornyl acrylate (1 g) and added to diurethane dimethacrylate, mixture of isomers, CAS 72869-86-4 (10 g). do The mixture can be stirred until homogenized and used directly for printing. can .

[0397] Formulation example 12 Initiator 2 (2 mg) was dissolved in ethanol (0.5 g) and added to a mixture of triethanolamine (1 g) and acrylamide / bisacrylamide (19 / 1; 40% aqueous solution, 10 g). doThe mixture can be stirred until homogenized and used directly for printing. can .

[0398] The above formulation was used for volumetric printing in a setup where a cuvette with four transparent windows was illuminated in one direction with a light sheet of wavelength 1, while an image of wavelength 2 was projected onto the light sheet from a different angle. will be While the cuvette or light sheet moves through the cuvette, the image is altered, generating a movie. do Printing allows solidification only in the volume where both wavelengths of light intersect. happen The remaining uncured resin is removed to form a molded body. obtain The molded body is then washed with a solvent and post-cured. to make Specifically, for a given example formulation, the following conditions are used: will be : Wavelength 1: 375 nm, Wavelength 2: 565 nm, Temperature 5°C, 25°C, or 45°C: Compounds 1-5 and 9-12 Wavelength 1: 405nm, wavelength 2: 565nm, temperature 25℃: Formulations 6, 7, 8 Xolography experiment (Figures 1 to 3) A portion of a mixture of pentaerythritol tetraacrylate (20 g), triethanolamine (1 g), and initiator 2 (2.3 mg) in 1.5 mL of ethanol was simultaneously illuminated by two LEDs with emission maxima at approximately 375 nm and 617 nm, respectively. do The light from the two LEDs is partially blocked by an opaque layer. will be The opaque layer can be changed during irradiation, for example with respect to its position. The material hardens at the point where both light beams hit the sample for a sufficient time. do After irradiation, the sample was washed with EtOH and the solid three-dimensional structure was obtain .

[0399] The features disclosed in the above description, in the claims and in the drawings may be suitable, individually or in any combination, for the realization of various designs. [Brief explanation of the drawings]

[0400] [Figure 1] 1 shows a schematic diagram of one embodiment of the process according to the present invention. [Figure 2] 1 shows a schematic diagram of the process according to the present invention. [Figure 3] 3 shows a perspective view of an embodiment of the inventive process shown in FIG. 2.

Claims

1. 1. A process for locally polymerizing a starting material by two-color photopolymerization using photoinitiator molecules, said process comprising the steps of: (i) providing a polymerizable starting material containing photoinitiator molecules, the photoinitiator molecule can be converted to a reactive state by sequential optical excitation; wherein, in the reactive state, the photoinitiator molecules locally induce polymerization of the starting material; (ii) photopolymerizing the starting material in a localized volume by irradiating the localized volume with light of a first wavelength and light of a second wavelength different from the first wavelength; (iii) converting the photoinitiator molecules from an initial state that does not substantially absorb light of the second wavelength to an intermediate state that has altered optical properties compared to the initial state, such that the photoinitiator molecules in the intermediate state absorb light of the second wavelength; (iv) absorbing light at the second wavelength to transition the photoinitiator molecules from the intermediate state to the reactive state and locally induce the polymerization; The photoinitiator molecule is represented by formula (II): 【Chemistry 1】 During the ceremony, X is selected from S, C, or N; Y is O, S, or NR ｃ and Y is selected from NR ｃ If NR ｃ The substituent R ｃ R represents a ring structure selected from the group consisting of benzimidazole, indoline, indole, dihydroquinoline, and tetrahydroquinoline. ８ containing the atoms necessary to complete it together; Z is N or CR ４ Selected from: R １ ~R １３ is H; D; halogen; NO ２ ; CN; OH; SH; substituted or unsubstituted C １ ~C ２０ Alkyl; substituted or unsubstituted C ３ ~C ２０ Cycloalkyl; substituted or unsubstituted C ６ ~C ４８ aryl; substituted or unsubstituted C ２ ~C ４２ Heteroaryl; substituted or unsubstituted C ２ ~C ４９ acyl substituted with alkyl groups; substituted or unsubstituted C6-C ４９ aryl-substituted acyl; substituted or unsubstituted C １ ~C ２０ Alkoxy; substituted or unsubstituted C ６ ~C ４８ Aryloxy; NH ２ ; substituted or unsubstituted C １ ~C ２０ Esters substituted with alkyl groups; substituted or unsubstituted C ６ ~C ４８ Aryl-substituted esters; substituted or unsubstituted C １ ~C ２０ Amides substituted with alkyl groups; substituted or unsubstituted C ６ ~C ４８ Aryl-substituted amide; NR' ２ , SiR' ３ , —O—SiR′ ３ (Wherein R' is a substituted or unsubstituted C １ ~C ２０ Alkyl and substituted or unsubstituted C ６ ~C ４８ aryl, wherein two R' may form a ring structure); substituted or unsubstituted carboxylic acids and salts thereof; substituted or unsubstituted sulfonic acids and salts thereof; substituted or unsubstituted sulfonic acid esters; substituted or unsubstituted sulfonic acid amides; formyl; ethers, thioethers; carbonates; carbonate esters; sulfates; boronic acids; boronic acid esters; phosphonic acids; phosphonic acid esters; phosphines; phosphates; peroxycarbonates; thiocarbonates; sulfinic acids; sulfinic acid esters; sulfonates; thiol esters; sulfoxides; sulfones ; Hydrazide; Thioaldehyde; Ketone; Thioketone; Oxime; Hydrazine; Nitroso; Azo; Diazo; Diazonium; Isocyanide; Cyanate; Isocyanate; Thiocyanate; Isothiocyanate; Hydroperoxide; Peroxide; Acetal; Ketal; Orthoester; Orthocarbonate Ester; Ammonium; Imine; Imide; Azide; Nitrate; Isonitrile; Nitrosoxy; Substituted or Unsubstituted Carbamate; Substituted or Unsubstituted Ether; Substituted or Unsubstituted Polyether Carbamate; Substituted or Unsubstituted Arylazo; Substituted or Unsubstituted C ２ ~C ２０ Alkynyl and substituted or unsubstituted C ２ ~C ２０ alkenyl; R １ ~R １３ When one or more substituents are present, the one or more substituents are selected from the group consisting of D; halogen; NO ２ ;CN;C ２ ~C ４９ Acyl substituted with alkyl group; substituted or unsubstituted C １ ~C ２０ Alkoxy; substituted or unsubstituted C ６ ~C ４８ aryloxy; substituted or unsubstituted C6-C ４９ Aryl-substituted acyl; (meth)acrylate; tosyl; NH ２ and OH; and / or R ５ ~R ８ two adjacent groups among R 12 and R 13 may be bonded to each other to form a fused ring structure; R １ ~R １３ is selected from one of the following structures: 【Chemistry 2】 During the ceremony, R １４ ~R １６ , R １９ When one or more substituents are present, the one or more substituents are selected from the group consisting of D; halogen; NO ２ ;CN;C ２ ~C ４９ Acyl substituted with alkyl group; substituted or unsubstituted C １ ~C ２０ Alkoxy; substituted or unsubstituted C ６ ~C ４８ aryloxy; substituted or unsubstituted C6-C ４９ Aryl-substituted acyl; (meth)acrylate; tosyl; NH ２ and OH; R １５ and R １６ may be joined together to form an unsubstituted or substituted ring structure; R １４ ~R １６ , R １９ is one of the following a), b) and c): a) R １９ is a substituted or unsubstituted C １ ~C １０ Alkyl; substituted or unsubstituted C ３ ~C １０ Cycloalkyl; substituted or unsubstituted C ６ ~C ３２ aryl; substituted or unsubstituted C ２ ~C ２８ Heteroaryl, substituted or unsubstituted C ２ ~C ２０ Alkynyl and substituted or unsubstituted C ２ ~C ２０ alkenyl, The substituents may be R to form a ring structure that forms an anthracene, thioxanthone, or fluorenone. ５ ~R ８ or R １０ ~R １３ may contain atoms necessary to complete with one of b) R １４ is NR' ２ wherein R′ is H, D, substituted or unsubstituted C １ ~C １０ Alkyl and substituted or unsubstituted C ６ ~C ３２ aryl, and two R' may form a ring structure); or OR' {wherein R' is H, D, substituted or unsubstituted C １ ~C １０ Alkyl; substituted or unsubstituted C ３ ~C １０ Cycloalkyl; substituted or unsubstituted C ６ ~C ３２ aryl; substituted or unsubstituted C ２ ~C ２８ Heteroaryl; SiR ３ wherein R″ is a substituted or unsubstituted C １ ~C １０ Alkyl and substituted or unsubstituted C ６ ~C ３２ aryl); R １５ and R １６ is H, D, CN, substituted or unsubstituted C １ ~C １０ Alkyl; substituted or unsubstituted C ３ ~C １０ Cycloalkyl; substituted or unsubstituted C ６ ~C ３２ aryl; substituted or unsubstituted C ２ ~C ２８ independently selected from heteroaryl; c) R １４ and R １５ is OR', where R' is H, D, substituted or unsubstituted C １ ~C １０ Alkyl; substituted or unsubstituted C ３ ~C １０ Cycloalkyl; substituted or unsubstituted C ６ ~C ３２ aryl; substituted or unsubstituted C ２ ~C ２８ heteroaryl); R １６ is H, D, CN, substituted or unsubstituted C １ ~C １０ Alkyl; substituted or unsubstituted C ３ ~C １０ Cycloalkyl; substituted or unsubstituted C ６ ~C ３２ aryl; substituted or unsubstituted C ２ ~C ２８ selected from heteroaryl; A process characterized by:

2. 10. The process of claim 1, wherein the light at the first wavelength and the light at the second wavelength are irradiated onto the localized volume simultaneously.

3. the light of the second wavelength is irradiated onto the local volume after irradiation of the light of the first wavelength on the local volume has ended; 3. The process of claim 1 or 2, wherein the light of the second wavelength is applied before the end of the decay time of the intermediate state of the photoinitiator molecules.

4. 4. The process of claim 1, wherein the photoinitiator molecules in the intermediate state do not substantially absorb light at the first wavelength.

5. 5. The process of claim 1, wherein in the volume that is desired not to polymerize, the photoinitiator molecules are converted from the intermediate state to the initial state by absorption of light at a third wavelength.

6. 6. The process of claim 1, wherein the photoinitiator molecules are converted to a reactive state by subsequent absorption of light at the second wavelength to induce polymerization in the localized volume.

7. the photoinitiator molecules are converted to a reactive state upon absorption of light at the second wavelength; 7. The process according to any one of claims 1 to 6, characterized in that this induces radical polymerization in said local volume.

8. 8. The process according to claim 1, wherein the photoinitiator molecules used in the process according to the invention comprise one or more of the following compounds: 【Transformation 3】 【change】 【change】 【change】 【change】 【change】 【change】 【change】 【change】

9. 9. The process according to any one of claims 1 to 8, characterized in that the polymerizable starting material further contains a coinitiator and / or a sensitizer.

10. 10. The process according to any one of claims 1 to 9, characterized in that the polymerizable starting material further contains an additive, an acid and / or a base.

11. 11. The process of claim 1, wherein the light beam of light at the first wavelength and the light beam of light at the second wavelength are irradiated so as to at least partially overlap in the localized volume.

12. said starting material is polymerized in several local volumes by photopolymerization; 12. The process according to claim 1, whereby a three-dimensional body is produced in the starting material.

13. 13. A process for 3D printing a shaped body, wherein the shaped body is manufactured by the process of any one of claims 1 to 12.

14. 14. An apparatus for locally polymerizing a starting material by carrying out a process of locally polymerizing a starting material by two-color photopolymerization using a photoinitiator molecule according to any one of claims 1 to 13, comprising: an intake for polymerizable starting material; light generating means configured to generate light at a first wavelength and light at a second wavelength different from said first wavelength; a light-directing device configured to irradiate a localized volume with light of the first wavelength and light of the second wavelength; The device is adapted to perform the following steps (i) to (iv): (i) introducing, by said intake port, said polymerizable starting material containing said photoinitiator molecules; the photoinitiator molecules can be excited by sequential optical excitation to a reactive state that locally initiates polymerization of the starting material; (ii) photopolymerizing the starting material in a localized volume by irradiating the localized volume with light of the first wavelength and light of the second wavelength; (iii) converting the photoinitiator molecules from an initial state that does not substantially absorb light of the second wavelength to an intermediate state that has altered optical properties compared to the initial state, such that the photoinitiator molecules in the intermediate state absorb light of the second wavelength; (iv) absorbing light at the second wavelength to transition the photoinitiator molecules from the intermediate state to the reactive state and locally induce the polymerization.

Images