Method and apparatus for localized polymerization of starting materials by bi-color photopolymerization

Abstract

The invention relates to a method and an apparatus for the localized polymerization of starting materials by two-color photopolymerization. In particular, photoinitiators are provided that cause curing of photopolymerizable formulations when irradiated with two different wavelengths and are useful in volume printing (volume initiators).

Description

[0001] This application is a divisional application of a Chinese invention patent application filed on June 8, 2020, with application number 202080041736.7 and invention name “Method and device for locally polymerizing starting materials by two-color photopolymerization and method for volumetric printing of a formed body”. Technical Field

[0002] The present invention relates to a method, an apparatus and a photo-switchable photoinitiator for local polymerization of a starting material by two-color photopolymerization and a method for volumetric printing of a shaped body (xolography). In particular, a photoinitiator is provided which causes the curing of a photopolymerizable formulation when irradiated with two different wavelengths and can be used for volumetric printing (xolocure initiator). Background Art

[0003] Definitions of photoswitching, photochromic structures, and terms used in this field can be found in [Bouas-Laurent, Dürr, Pure and Applied Chemistry, 2001, 73, 639-665]. Generally, a photoswitchable is a photochromic compound that is capable of undergoing a reversible structural change in at least one direction via a photochemical pathway. A typical example is the spiropyran / merocyanine system, as shown below:

[0004]

[0005] The colorless spiropyran is the thermodynamically favored form and undergoes a ring-opening reaction upon irradiation with UV light to a metastable colored merocyanine form (positive photochromic). The merocyanine form can be a mixture of four different isomers. In this patent, the term merocyanine refers to one or more different E / Z isomers. The reverse reaction from merocyanine to spiropyran can be performed photo- or thermally (T-type photochromic). Spiropyran photoswitching belongs to the group of chromene-based switching, which are typically positive and T-type photochromic.

[0006]

[0007] In this type of chromene-based photoswitching, R and R' can be alkyl, alkynyl or aryl substituents, and X can be a carbon or nitrogen atom. Various derivatives of this family are photochromic, in which the aryl moiety is further substituted, or the oxygen atom is changed to a nitrogen atom. The double bond in the open form can be in E and / or Z configuration.

[0008] An overview of photoinitiators and terminology and definitions can be found in [Green, Industrial Photoinitiators A Technical Guide, CRC Press, 2010; Fouassier and Lalevée, Photoinitiators for Polymer Synthesis: Scope, Reactivity and Efficiency, Wiley VCH, 2012]. Curing of a material refers to the polymerization of the monomers. Depending on the polymerization mechanism, a variety of functional groups have been found to be suitable monomers, including but not limited to acrylates / esters, methacrylates / esters, thiols + alkenes, epoxides, oxiranes, oxetanes or vinyl ethers. Photoinitiators initiate polymerization upon exposure to light. Polymerization can be free radical, cationic, anionic or metal catalyzed. Photoinitiators are either type 1, in which a single compound is able to initiate polymerization, or type 2, in which a co-initiator is required. Type 1 photoinitiators can perform homobond cleavage (free radicals) or heterobond cleavage (cations / anions) to form reactive species. In the following reaction, other species can be produced, which can lead to different properties of polymerization, such as amine radicals are initially produced by homobond cleavage, and then hydrogen atoms are captured from the environment to form amines and start base-mediated polymerization. Type 2 photoinitiators can start polymerization by two different mechanisms, the first of which is to capture hydrogen from a co-initiator, produce two free radicals and can produce more reactive species from subsequent reactions. The second mechanism is a photoredox reaction, in which electrons are transferred between a co-initiator and a photoinitiator. The photoredox reaction can be carried out by a further proton transfer reaction to produce free radicals or other subsequent reactions, thereby producing further reactive species, such as acids, bases or free radicals. A variety of structural units are known to initiate polymerization, and examples of the most important structural units are shown below.

[0009]

[0010] Additive manufacturing or 3D printing can be performed using a variety of techniques and materials and enables the manufacture of customized parts. Compared to injection molding, additive manufacturing enables the formation of more complex structures, resulting in material savings and the opportunity to build specialized parts for machines with superior performance. However, most additive manufacturing techniques rely on a layer-by-layer build sequence. Therefore, the object is cut into many layers and printed one after another. Therefore, certain limitations are inherent and support structures are required to prevent overhanging parts from falling off. Typically, several mechanical steps are involved between the printing of the layers, which leads to long manufacturing times. The form of the starting material for printing must enable mechanical manipulation without destroying the object, which limits the starting material to a specific powder size or viscosity.

[0011] One of the most prominent 3D printing technologies is stereolithography [Hull, US4575330, 1984] and technologies related to stereolithography. Typically, a thin layer of photocurable resin is irradiated with a specific pattern of light of one wavelength. This causes photopolymerization and results in hardening of the irradiated areas. A new layer of photocurable resin is then introduced from the top or bottom of the previous layer and the irradiation causes the layer to cure. The advantages of irradiation-based technologies are the fast process of photopolymerization and the high resolution in which light can be applied to the layers and a certain flexibility in terms of material properties. Although stereolithography is a well-known technology, the disadvantages mentioned above still exist. Stereolithography requires support structures, which makes delicate post-processing necessary. Although photopolymerization is fast, the slow mechanical process from one layer to the next reduces the overall manufacturing speed of stereolithography. In addition, the resin must meet specific criteria, such as low viscosity to achieve flow and homogeneity of the layers, and high absorption at the irradiation wavelength to avoid curing in the first few layers. The requirements for high resolution and low viscosity of thin layers lead to high oxygen and water concentrations at the surface. Water quenches cationic polymerization processes, while oxygen quenches free radical processes. While the latter can be improved by adding amines, the resins require high concentrations of expensive photoinitiators to overcome this inhibition process, but still produce less cross-linked material and therefore less strong.

[0012] To overcome the limitations of stereolithography, volumetric printing has been proposed as a solution. In this type of method, the resin is in a container and curing by the action of light does not take place on the walls of the container, but inside the volume. This eliminates the necessity for support structures, enables the use of low and high viscosity resins, enables the formation of soft objects, and is not inhibited by oxygen or water.

[0013] One implementation of volume printing relies on two-photon polymerization, in which common photoinitiators are excited by the simultaneous uptake of two photons, causing polymerization at the focus of the laser beam [S. Maruo et al., Optics Express (Opt. Lett.), 1997, 22, 132-134]. Two-photon polymerization requires expensive and sophisticated equipment with an intense pulsed laser source. In addition, due to the nonlinearity of the process, the technique is inherently slow, which significantly reduces the achievable object size.

[0014] In addition, tomographic reconstruction methods have been developed in which the resin is illuminated with different light patterns from different angles. Due to the superposition of light, an intensity distribution is generated in the volume, which leads to solidification wherever a certain threshold is exceeded. The light pattern required to form a three-dimensional object is calculated in advance in a manner similar to the inverse process of computed tomography analysis [Kelly et al., US20180326666A1, 2018; Shusteff et al., US20180015672A1, 2018; Delrot et al., WO2019043529A1, 2019]. This technique has the inherent disadvantage of matching the hardening threshold at every location in the volume. In addition, the resin rotates, causing diffusion when solidifying. Both effects lead to low resolution and object size. In addition, this technique is not able to produce objects with sharp edges and is therefore limited to the circular surfaces of the printed parts.

[0015] In order to overcome the problems of two-photon polymerization and tomographic reconstruction, a two-color photoinitiation system can be envisaged. This requires a photoinitiator that transforms from its thermodynamically stable ground state form A to a metastable ground state species B when irradiated by light of a first wavelength λ1. When species B absorbs light of a second wavelength λ2, it is able to initiate polymerization via form C. Form C is an excited state of B, which produces free radicals, cations or anions by further reaction with or without a co-initiator. In the sense of the present invention, the terms first wavelength, second wavelength and third wavelength may refer to wavelength ranges. For use in volumetric printing methods, the reverse reaction from B to A must be possible to avoid hardening of unwanted areas. The reverse reaction from B to A can be triggered by thermal triggering or by irradiation with a third wavelength λ3.

[0016]

[0017] There are two unwanted reaction pathways that may lead to polymerization using only the first wavelength. A may directly initiate polymerization without switching, or B may absorb photons of the first wavelength and initiate polymerization. An ideal two-color photoinitiator suitable for volumetric printing would not suffer from these unwanted reactions and would be thermally reversible or could be switched back by irradiation with a third wavelength. The following examples are related to photoinitiators and multi-wavelength irradiation, but they all suffer from unwanted side reactions and / or lack of thermal reversibility. So far, no three-dimensional objects have been fabricated, except for single voxels, which do not require any thermal or photochemical reverse reactions and are insufficient for volumetric printing.

[0018] The related concept was first proposed by Swainson in a series of patents [Swainson, US4041476, US4078229, US4238840, US4466080, US4471470, US4333165] and subsequently by Lippert (US2020 / 0108557A1). Several theoretical approaches were presented, in which photoinitiators were thought to react to two or three different wavelengths. However, although the concept was interesting, none of the molecules described in the patents showed a response to two different wavelengths to initiate polymerization, and they were neither feasible nor commercially satisfactory for volume printing.

[0019] JP H0375127A to Kenji and Ichiro claims three light switches for volume printing. The molecules described therein are known for their photochromic properties, but do not exhibit selective curing, where beams of two wavelengths intersect, as shown by Neckers [US005230986A, col. 6, lines 27-35]. Even if they can be initiated with two-color irradiation, they show a slow thermal reverse reaction from B to A, which makes them unsuitable for volume printing applications.

[0020] Barachevsky et al. [US7244548B2, 2007] and Waldman et al. [US2009 / 0202919A1] disclose several initiators for recording phase holograms. In this type of application, the curable composition is first irradiated with one wavelength to induce isomerization from A to B. Later, a second wavelength can be used to record a phase hologram by initiating polymerization. This application requires a photoinitiator that responds to two different wavelengths but does not show a thermal reverse reaction from B to A. The lack of a thermal reverse reaction makes the disclosed initiators unsuitable for volume printing methods.

[0021] US005230986A to Neckers discloses iodinated benzospiropyrans with suitable co-initiators as two-photon free radical photoinitiators having the following structure, wherein at least one of the two substituents X1 and X3 is iodine:

[0022] .

[0023] The disclosed molecules have limited efficiency for photopolymerization, which necessitates high concentrations [Lee, Neckers, Chem. Mater. 1991, 3, 852-858 and Lee, Neckers, Chem. Mater. 1991, 3, 858-864]. Therefore, the penetration depth of light is limited and the volume suitable for printing cannot exceed 2 mm, as shown by the authors [Lee, Neckers, Chem. Mater. 1991, 3, 858-864, Figures 12 and 13]. The iodine substituent acts as a triplet sensitizer on the spiropyran form, so that only the unwanted side reactions generated by the first wavelength of irradiation dominate, in which the spiropyran causes a photoredox reaction and thus forms free radicals, without isomerizing to merocyanine. Iodinated benzospiropyrans are further limited by a slow thermal reverse reaction, which makes them unsuitable for volume printing.

[0024] Two other two-component systems based on spiropyran have been reported for recording holograms [Jeudy, Robillard, Opt. Commun. 1975, 13, 25-28; Ichimura, Sakuragi, J. Polym. Sci. Polym. Lett, 1988, 26 185-189]. However, both are not suitable for volume printing because, on the one hand, the thermal back reaction in both cases is too slow for commercially successful applications, and on the other hand, both lead to substantial polymerization only at the first wavelength [Lee, Neckers, Chemistry of Materials 1991, 3, 858-864].

[0025] The object of the present invention is to overcome the disadvantages of currently available methods as discussed above. More particularly, the object of the present invention is to provide a method, an apparatus and a photo-switchable photoinitiator for local polymerization of a starting material by two-color photopolymerization and a method for volumetric printing of a shaped body, which enables flexible and locally targeted curing in the starting material by photopolymerization (xolography). The technology will be particularly suitable for 3D printing. More particularly, a photoinitiator will be provided, which causes curing of a photopolymerizable formulation when irradiated with two different wavelengths and can be used for volumetric printing (xolocure initiator). Summary of the invention

[0026] For the solution, there is provided a method for locally polymerizing a starting material by two-color photopolymerization according to independent items 1 and 21. In addition, there is provided a method for 3D printing a formed body according to item 20. Other embodiments belong to the dependent items.

[0027] According to one aspect, a method for locally polymerizing a starting material by two-color photopolymerization is provided. A polymerizable starting material is provided, which contains photoinitiator molecules that can be converted into a reactive state by sequential light excitation of multiple wavelengths, wherein the photoinitiator molecules locally trigger polymerization of the starting material, in particular local curing or hardening of the starting material due to polymerization. The starting material is photopolymerized in the local volume by irradiating the local volume with light of a first wavelength and light of a second wavelength different from the first wavelength simultaneously or successively.

[0028] In the local volume, by absorbing photons of the first wavelength, the photoinitiator molecules are transformed from an initial state in which the photoinitiator molecules do not substantially absorb light of the second wavelength to an intermediate state having optical properties different from the initial state in the following manner: the photoinitiator molecules in the intermediate state absorb the light of the second wavelength and enter a reaction state. In the local volume, due to the gradual absorption of the light of the first wavelength and the light of the second wavelength, the photoinitiator molecules are transformed from the initial state to the reaction state via the intermediate state, thereby locally triggering polymerization. Outside the local volume, the photoinitiator molecules in the intermediate state return to the initial state.

[0029] According to another aspect, a device for locally polymerizing a starting material by two-color photopolymerization is created. The device comprises the following: an inlet for a polymerizable starting material; a light generating unit arranged to provide light of a first wavelength and light of a second wavelength, the second wavelength being different from the first wavelength; and a light guiding unit arranged to irradiate the light of the first wavelength and the light of the second wavelength into a local volume. The device is arranged to perform the following procedure: introducing a polymerizable starting material through the inlet, the starting material comprising photoinitiator molecules, the photoinitiator molecules being capable of being transformed into a reaction state by sequential photoexcitation, in which the photoinitiator molecules locally trigger polymerization of the starting material, thereby causing photopolymerization of the starting material in the local volume by irradiating the light of the first wavelength and the light of the second wavelength in a defined local volume. In the local volume, the following is provided: the photoinitiator molecules are transformed from an initial state in which the photoinitiator molecules do not substantially absorb the second light due to the absorption of photons of the first wavelength to an intermediate metastable ground state having changed optical properties compared to the initial state in such a way that the photoinitiator molecules in the intermediate state absorb the light of the second wavelength. In the local volume, due to the gradual absorption of the light of the first wavelength and the light of the second wavelength, the photoinitiator molecules are transformed from the initial state to the reaction state via the intermediate state, thereby locally triggering polymerization. Outside the local volume, the photoinitiator molecules in the intermediate state return to the initial state.

[0030] Furthermore, a method for volumetric printing of a shaped body is provided, wherein the shaped body is produced by a method for local polymerization of a starting material, wherein the local photopolymerization leads to hardening or solidification of the starting material and thus to production of the shaped body.

[0031] The absorption capacity of the photoinitiator molecules in the intermediate state for light of the second wavelength may be based on a change in the optical properties of the photoinitiator molecules, whereby the absorption capacity for light of the second wavelength is initially formed, in particular due to the transition from the initial state to the intermediate state, a spectral absorption band is formed in the second wavelength region. Alternatively, it can be provided that the absorption band of light of the second wavelength that already exists in the initial state of the photoinitiator molecules is enhanced or expanded in the intermediate state.

[0032] In the intermediate state, the photoinitiator molecules may still absorb or no longer absorb within the first wavelength range. More preferably, the photoinitiator molecules in the intermediate state may not substantially absorb light of the first wavelength. Most preferably, the photoinitiator molecules in the intermediate state may not absorb light of the first wavelength.

[0033] In one aspect, the intermediate state can be thermally returned to the initial state at the printing temperature. More preferably, the intermediate state can be thermally returned to the initial state at the printing temperature at a temperature higher than k=0.01 s -1More preferably, the rate constant of the thermal reverse reaction is higher than 0.02 s -1 Even more preferably, the rate constant of the thermal reverse reaction is higher than 0.05 s -1 Most preferably, the rate constant of the thermal reverse reaction is higher than 0.08 s -1 .

[0034] In various embodiments, localized photopolymerization in the localized areas can result in hardening or curing of the starting material.

[0035] Light of the first and second wavelengths may be simultaneously illuminated into the local volume.

[0036] After the irradiation of the local volume with light of the first wavelength ends, light of the second wavelength may be irradiated into the local volume, and the light of the second wavelength is irradiated before the decay time of the intermediate state of the photoinitiator molecule ends.

[0037] Due to the absorption of the light of the second wavelength, the photoinitiator molecules can be transformed into a reactive state, thereby triggering polymerization in the local volume. It can be expected that the reactive state is similar to a Norrish I type reaction or a Norrish II type reaction known to the skilled person. Alternatively, it can be expected that the reactive state undergoes an electron transfer reaction using a co-initiator.

[0038] Disclosed are additional dual-color photoinitiators that respond to electromagnetic radiation of a first wavelength by switching from a thermodynamically stable state A to a metastable state B. B is capable of absorbing electromagnetic radiation of a second wavelength, thereby forming C, which is capable of initiating a polymerization reaction. B can undergo a rapid thermal reverse reaction to form A and then be inactivated by electromagnetic radiation of a second wavelength. The use of such dual-color photoinitiators enables photopolymerizable resins to be cured in any volume where two wavelengths of electromagnetic radiation intersect, for example, where an image is projected on a light sheet. The disclosed substitution pattern ensures rapid thermal reverse reaction and does not cure with only the first wavelength, thereby preventing curing in unwanted areas. The use of the disclosed dual-color photoinitiator in a polymerizable mixture enables rapid volumetric printing at high resolution. No support structure is required, which saves material and enables the manufacture of soft and fragile products. Since the quenching of polymerization by oxygen and water is minimized, a wide range of possible resin viscosities can be covered and high reactivity can be achieved. Due to less mechanical manipulation, the use of the disclosed dual-color photoinitiator enables faster printing than additive manufacturing techniques based on ordinary photopolymerization.

[0039] The disclosed dual-color photoinitiator is characterized by a manner in which polymerization is induced when electromagnetic radiation of two different wavelengths interacts with the same volume of polymerizable material in a simultaneous or sequential manner. In a volume interacting with electromagnetic radiation of only one wavelength, polymerization is not induced.

[0040] The disclosed dual-color photoinitiator in thermodynamically stable form A absorbs photons from electromagnetic radiation of a first wavelength, which induces an isomerization reaction to a metastable form B. The dual-color photoinitiator in metastable form B absorbs photons from electromagnetic radiation of a second wavelength, which leads to an excited state C and further leads to the formation of free radicals by: hydrogen abstraction from a co-initiator followed by electron transfer or decomposition to free radicals; electron transfer followed by hydrogen abstraction or decomposition to free radicals; or homobond cleavage to form free radicals before or after other rearrangement reactions. The dual-color photoinitiator in metastable state B that does not absorb photons from electromagnetic radiation of the second wavelength spontaneously returns to thermodynamically stable state A by a thermal process.

[0041] The dual-color photoinitiator carries a carbonyl functional group, which is a weak triplet sensitizer of spiropyrans and related structures, and therefore exhibits no curing with ultraviolet light alone. Electromagnetic radiation of a first wavelength results in the excitation of an initiator in form A and switching to an initiator in form B primarily through a singlet state. The efficient ring-opening reaction of the photoswitch motif prevents the dual-color initiator from forming free radicals by irradiation with only the first wavelength. The merocyanine form B can act as an internal triplet sensitizer when irradiated with a second wavelength, which results in the carbonyl group abstracting a hydrogen atom from the co-initiator, undergoing an electron transfer reaction, or undergoing a homobond cleavage. The substituents are selected in such a way that the absorption of the merocyanine form B at the first wavelength is minimized or eliminated, and form B is thermodynamically unstable to ensure a rapid thermal reverse reaction from B to A. In addition, the disclosed dual-color initiator benefits from the extremely low or negligible quantum yield of the competitive photoreaction from B to A and the high extinction coefficient of the B form, where form A does not absorb. The merocyanine form B generally has broad absorption in the visible region, which enables high intensity over a wide wavelength range.

[0042] Suitable dual-color photoinitiators have the following structure represented by the following formula (I):

[0043] (I)

[0044] Where R a and R b are independently selected from unsubstituted or substituted aryl, unsubstituted or substituted alkynyl or are linked to each other to form an unsubstituted or substituted ring structure, and Y is selected from O, S or N; when Y is N, the substituent contains a 8The atoms required to form a cyclic structure selected from benzimidazole, indoline, indole, dihydroquinoline and tetrahydroquinoline; wherein Z is selected from N or CR 4 ; where R 3 To R 8 independently selected from 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 Aryl acyl; 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 ester; substituted or unsubstituted C1-C 20 Alkylamide; substituted or unsubstituted C6-C 48 Arylamide; NR'2, SiR'3, -O-SiR'3, wherein R' is independently selected from substituted or unsubstituted C1-C 20 Alkyl and substituted or unsubstituted C6-C 48 Aryl, two R' can form a ring structure; substituted or unsubstituted carboxylic acid and its salt; substituted or unsubstituted sulfonic acid and its salt; substituted or unsubstituted sulfonic acid ester; substituted or unsubstituted sulfonamide; formyl; ether, thioether; carbonate / ester group; carbonate ester; sulfate / ester group; boric acid; borate ester; phosphonic acid; phosphonate; phosphine; phosphate / ester group; peroxycarbonic acid; thiocarbonic acid; sulfinic acid; sulfinic acid ester; sulfonate / ester group; thioester, sulfoxide; sulfone; hydrazide; thialdehyde; ketone; thioketone; oxime; hydrazine; nitroso; azo; diazo; diazo ; isocyanide; cyanate / ester; isocyanate / ester; thiocyanate / ester; isothiocyanate / ester; hydrogen peroxide; peroxide; acetal; ketal; orthoester; orthocarbonate; ammonium; imine; imide; azide; nitrate / ester; isonitrile; nitroso; substituted or unsubstituted carbamate / ester; substituted or unsubstituted ether; substituted or unsubstituted polyether carbamate / ester; substituted or unsubstituted arylazo; substituted or unsubstituted C2-C 20 Alkynyl and substituted or unsubstituted C2-C 20 alkenyl; wherein one or more substituents, if present in R 3 -R 8One or more of the following are independently selected from D; halogen; NO2; CN, C2-C 49 Alkyl acyl; substituted or unsubstituted C1-C 20 Alkoxy; substituted or unsubstituted C6-C 48 Aryloxy; substituted or unsubstituted C2-C 49 Aryl acyl; (meth) acrylate / ester; tosyl; NH2; and OH; and / or two adjacent R 5 -R 8 The groups may be linked to each other to form a fused ring structure, preferably a fused aromatic C6 ring; and

[0045] Where R 3 -R 8 At least one of the following structures is selected from:

[0046] , , , , , , ,

[0047] Where R 14 To R 25 independently selected from 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 Aryl acyl; 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 ester; substituted or unsubstituted C1-C 20 Alkylamide; substituted or unsubstituted C6-C 48 Arylamide; NR'2, SiR'3, -O-SiR'3, wherein R' is independently selected from substituted or unsubstituted C1-C 20 Alkyl and substituted or unsubstituted C6-C 48Aryl, two R' can form a ring structure; substituted or unsubstituted carboxylic acid and its salt; substituted or unsubstituted sulfonic acid and its salt; substituted or unsubstituted sulfonic acid ester; substituted or unsubstituted sulfonamide; formyl; ether, thioether; carbonate / ester group; carbonate ester; sulfate / ester group; boric acid; borate ester; phosphonic acid; phosphonate; phosphine; phosphate / ester group; peroxycarbonic acid; thiocarbonic acid; sulfinic acid; sulfinic acid ester; sulfonate / ester group; thioester, sulfoxide; sulfone; hydrazide; thialdehyde; ketone; thioketone; oxime; hydrazine; nitroso; azo; diazo; diazo ; isocyanide; cyanate / ester; isocyanate / ester; thiocyanate / ester; isothiocyanate / ester; hydrogen peroxide; peroxide; acetal; ketal; orthoester; orthocarbonate; ammonium; imine; imide; azide; nitrate / ester; isonitrile; nitroso; substituted or unsubstituted carbamate / ester; substituted or unsubstituted ether; substituted or unsubstituted polyether carbamate / ester; substituted or unsubstituted arylazo; substituted or unsubstituted C2-C 20 Alkynyl and substituted or unsubstituted C2-C 20 alkenyl; wherein one or more substituents, if present in R 14 -R 25 One or more of the following are independently selected from D; halogen; NO2; CN, C2-C 49 Alkyl acyl; substituted or unsubstituted C1-C 20 Alkoxy; substituted or unsubstituted C6-C 48 Aryloxy; substituted or unsubstituted C2-C 49 aryl acyl; (meth) acrylate; tosyl; NH2; and OH; and R 15 and R 16 They 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.

[0048] Preferably, a suitable dual-color photoinitiator may have a structure represented by the following formula (II):

[0049] (II)

[0050] Where X is selected from S, CR 1 R 2 or NR 1 ; Y is selected from O, S or NR c ; When Y is N, the substituent R c Contains for use with R 8 The atoms required to form a ring structure selected from benzimidazole, indoline, indole, dihydroquinoline and tetrahydroquinoline; Z is selected from N or CR 4 ; and R 1 To R 13As for R in the above formula (I), 3 To R 8 are independently selected as defined in .

[0051] Preferably, R a and R b are independently selected from substituted or unsubstituted C6-C 14 Aryl and substituted or unsubstituted C2-C 10 More preferably, R a and R b Independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl and C2-C5 alkynyl.

[0052] Preferably, X is selected from S or CR 1 R 2 More preferably, X is C and R 1 and R 2 Can be independently selected from H, D, C1-C4 alkyl. More preferably, R 1 and R 2 It's methyl.

[0053] Preferably, Z is CR 4 More preferably, Z is C and R 4 Can be independently selected from H, D, CN, Cl-C 12 Alkyl, fluorinated C1-C 12 Alkyl or C6-C 14 More preferably, R 3 and R 4 It's H.

[0054] Preferably, R 9 R may be selected from H, D, substituted or unsubstituted C1-C4 alkyl, phenyl and benzyl. More preferably, R 9 It is methyl, -CH2-CH2-OH, phenyl or benzyl.

[0055] Preferably, R 10 To R 13 Can be independently selected from H, D, C1-C4 alkyl.

[0056] Preferably, R 14 can be selected from H, methyl, halogen, more preferably, R 14 , R 15 and R 16 Can be independently selected from H, methyl, halogen. More preferably, R 14 , R 15 and R 16 It's chlorine.

[0057] Preferably, R 14 , R 15and R 16 can be independently selected from 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, more preferably, R 14 , R 15 and R 16 It may be selected from methyl, phenyl or substituted phenyl.

[0058] In another preferred embodiment, R 14 It may be NR'2, wherein R' may be independently selected from H, D, substituted or unsubstituted C1-C 10 Alkyl and substituted or unsubstituted C6-C 32 Aryl, and two R' can form a ring structure; R 15 and R 16 can be independently selected from 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 It can be NR'2, wherein R' can be independently selected from substituted or unsubstituted C1-C 10 Alkyl, two R' can form a ring structure; R 15 and R 16 may be independently selected from substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C 10 Cycloalkyl; substituted or unsubstituted C6-C 32 Most preferably, R 14 It can be NR'2, wherein R' can be methyl, ethyl, or two R's form morpholine; R 15 and R 16 Independently selected from methyl, ethyl and benzyl.

[0059] In another preferred embodiment, R 14 It can be OR', wherein R' is selected from 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, SiR''3, wherein R'' is independently selected from substituted or unsubstituted C1-C10 Alkyl and substituted or unsubstituted C6-C 32 Aryl, R 15 and R 16 can be independently selected from 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 It can be OR', wherein R' is independently selected from H, D, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, SiR''3, wherein R'' is independently selected from substituted or unsubstituted C1-C 10 Alkyl and substituted or unsubstituted C6-C 32 Aryl. 15 and R 16 may be independently selected from substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C 10 Cycloalkyl; substituted or unsubstituted C6-C 32 Most preferably, R 14 is OR', wherein R' is methyl, ethyl, benzyl or trimethylsilyl; and R 15 and R 16 Independently selected from methyl, ethyl, phenyl and benzyl.

[0060] In another preferred embodiment, R 14 and R 15 It can be OR', wherein R' is independently selected from 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, R 16 It can be selected from 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 It can be OR', wherein R' is independently selected from H, D, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C3-C10 cycloalkyl; and R 16 Can be selected from substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C3-C 10 Cycloalkyl; substituted or unsubstituted C6-C 32 Most preferably, R 14 and R 15 can be OR', wherein R' is H, methyl, ethyl or benzyl; and R 16 It may be selected from methyl, ethyl, phenyl and benzyl.

[0061] Preferably, R 17 Can be selected from 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 selected from 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, the substituent may contain 5 -R 8 or R 10 -R 13 More preferably, R 17 Selected from substituted or unsubstituted C1-C 10 Alkyl; substituted or unsubstituted C6-C 32 Aryl; OR', wherein R' is selected from H, substituted or unsubstituted C1-C 10 Most preferably, R 17 It may be methyl, ethyl, phenyl, methoxy or ethoxy.

[0062] Preferably, R 18 It can be O or NR', wherein R' is selected from substituted or unsubstituted C1-C 20 Alkyl esters; substituted or unsubstituted C6-C 48 More preferably, R 18 It can be O or NR', where R' is a substituted or unsubstituted C6-C 48 Most preferably, R 18It can be O or NR', where R' is a phenyl ester or a tolyl ester.

[0063] Preferably, R 19 Can be selected from 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 The substituent may contain 5 -R 8 or R 10 -R 13 One of the atoms in the ring structure is used to form anthracene, thioxanthone or fluorenone, more preferably, R 19 It may be selected from substituted or unsubstituted phenyl or naphthyl.

[0064] Preferably, R 20 and R 21 may be independently selected from substituted or unsubstituted C6-C 32 Aryl; substituted or unsubstituted C2-C 28 heteroaryl, OR', wherein R' is selected from 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 The groups may be independently selected from phenyl, tolyl, methoxy and ethoxy.

[0065] Preferably, R 22 , R 23 and R 24 may be independently selected from 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, more preferably, R 22 , R 23 and R 24 May be independently selected from methyl, ethyl or phenyl.

[0066] Preferably, R 25 Can be selected from substituted or unsubstituted C6-C 32Aryl; substituted or unsubstituted C2-C 28 heteroaryl, OR', wherein R' is selected from 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 It may be selected from phenyl, tolyl, methoxy and ethoxy.

[0067] The halogen here may be fluorine, chlorine, bromine or iodine.

[0068] The alkyl, alkenyl and alkynyl groups here may be cyclic, straight-chain or branched.

[0069] Here, the alkyl acyl group has the formula

[0070]

[0071] and the aryl acyl group has the formula

[0072]

[0073] The wavy line represents the bond between the acyl group and the structure of formula (I).

[0074] In the group R1-R 13 In case one (or more) of the is selected to be an amide, the bond can be formed through N as well as through CO.

[0075] In the group R1-R 13 In case one (or more) of the is chosen to be an ester, the bond can be formed through O as well as through CO.

[0076] 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 them is a substituted or unsubstituted C2-C 49 Aryl acyl.

[0077] In another embodiment, R 1 and R 2 Independently selected from C1-C 20 Alkyl, or C1-C 12 Alkyl, or C1-C8 alkyl, or C1-C4 alkyl, or methyl.

[0078] In another embodiment, R 3 -R 8 and R 10 -R 13 are independently selected from H, D, halogen, NO2, CN, substituted or unsubstituted C2-C 49 Alkyl acyl; substituted or unsubstituted C2-C 49 Aryl acyl, substituted or unsubstituted aryl, NH2 and OH, wherein one or more substituents, if present, are selected from halogen, NO2, CN, NH2 and OH.

[0079] In another embodiment, the proviso is that R 3 -R 8 and R 10 -R 13 are independently selected from H and electron withdrawing groups.

[0080] In which the group R 1 -R 13 In all embodiments in which one or more of is selected from halogen, there may be a proviso that the halogen is F (fluorine).

[0081] In one embodiment, R 12 and R 13 Can be linked together to form a fused aromatic C6 ring.

[0082] In one embodiment, R 10 -R 13 The two of them can be linked together to form a fused aromatic C6 ring and R 5 -R 9 One of them is selected from unsubstituted or substituted aryl acyl; or unsubstituted or substituted alkyl acyl.

[0083] In one embodiment, R 10 -R 13 are independently selected from H and electron withdrawing groups, and R 5 -R 8 One of them is selected from unsubstituted or substituted aryl acyl; or unsubstituted or substituted alkyl acyl.

[0084] Typical electron withdrawing groups can be CN, F, NO2, ester, acyl, SO2R such as SO2CF3, SO2Me or SO2NH2, SF5, NR3 + , pyridine , halogen, and fluorinated alkyl or aryl groups such as CF3.

[0085] In one embodiment, R 5 -R 8At least one of them is independently selected from electron donating groups, or selected from alkoxy groups, or R 8 is a methoxy group, and R 5 -R 8 , R 10 -R 13 At least one of them is selected from unsubstituted or substituted aryl acyl; or unsubstituted or substituted alkyl acyl.

[0086] Typical electron donating groups can be SH, SR, OH, OR, NH2, NHR and NR2.

[0087] In a specific embodiment, the condition may be R 6 , R 7 and R 12 independently selected from CF3, SO2Me, SO2NH2, CN, F, NO2, C6 aryl, unsubstituted C6 aryl acyl of the formula

[0088] ,

[0089] A dimethoxy-substituted aryl acyl group of the formula

[0090] ,

[0091] A methoxy-substituted aryl acyl group of the formula

[0092] ,

[0093] A fluorine-substituted aryl acyl group of the formula

[0094] ,

[0095] Or the following

[0096] ,

[0097] and C6 aryl.

[0098] In another embodiment, the condition may be that R9 is selected from C1-C 20 Alkyl and C6-C 48 Aryl, or selected from C1-C8 alkyl and C6-C 18 Aryl, or selected from C1-C4 alkyl and C6-C 12 Aryl or selected from methyl, benzyl and phenyl.

[0099] In one embodiment, the dual-color photoinitiator may be linked to a polymerizable group. The polymerizable group may be selected from (meth)acrylate groups, acrylamides, vinyl ethers, and vinyl esters, preferably (meth)acrylate groups.

[0100] In another embodiment, two or more dual-color photoinitiators can be connected to each other through a linking group. The chemical bond to the linking group can be independently composed of R 1 -R 13 Any one of them is established, preferably by R 9 Establish.

[0101] In another embodiment, the proviso is that R 10 -R 13 are independently selected from H and electron withdrawing groups and R 3 -R 8 are independently selected from H and substituents belonging to the formula:

[0102] , , , , , , ,

[0103] More specifically R 12 is an electron-withdrawing group, and R 6 is a substituted or unsubstituted aryl acyl group, wherein the aryl acyl group may be unsubstituted or substituted with electron withdrawing or electron donating substituents, for example:

[0104] , , ,

[0105] Or, R 6 is an α-aminoacyl group, an α-hydroxyacyl group or an α-alkoxyacyl group:

[0106] , , ,

[0107] In another embodiment, the proviso is that R 3 -R 8 and R 10 -R 13 At least two of are independently selected from substituents belonging to the following formula:

[0108] , , , , , , ,

[0109] More specifically R 6 and R 12 is a substituted or unsubstituted aryl acyl group, or R6 and R 12 is an α-aminoacyl group, an α-hydroxyacyl group or an α-alkoxyacyl group:

[0110] , ,

[0111] Among them, R', R 15 , R 16 R' is independently selected from H, D, unsubstituted or substituted aryl; or unsubstituted or substituted alkyl, more preferably selected from methyl, ethyl, benzyl, phenyl, tolyl. Two R's may form a ring structure.

[0112] In another embodiment, provided that the substituent R 3 -R 8 and R 10 -R 13 One of them is selected from the substituents belonging to the following formula:

[0113] , , , , , , ,

[0114] The substituent R 14 -R 25 One of them contains an atom of the second photoswitchable group.

[0115] In another embodiment, the condition may be that the substituent R 1 -R 13 One of them contains a functional group that increases solubility in water. Such functional groups may in particular be salt-forming ionic functional groups, such as ammonium or sulfonate / ester groups; polyethylene glycol or polar functional groups, such as OH, NH2, SO2NH2.

[0116] In one embodiment, R 5 and R 7 are independently selected from H and electron donating groups, more preferably H, methyl, methoxy and R 6 Has the following formula:

[0117] or

[0118] Where R 20 and R 21 or R 25 Independently selected from aryl or alkoxy, more preferably selected from phenyl, ethoxy, methoxy.

[0119] In another embodiment, the proviso is that R10 -R 13 are independently selected from H and electron withdrawing groups and R 5 -R 8 are independently selected from H and substituents belonging to the formula:

[0120] ,

[0121] Where R 14 -R 15 Independently selected from halide, alkyl or aryl, more preferably selected from chlorine, methyl, ethyl, phenyl, tolyl.

[0122] In a particularly preferred embodiment, the photoinitiator molecule used in the method according to the present invention comprises one or more of the following compounds 1 to 80.

[0123] 1 2

[0125] 3 4

[0127] 5 6

[0129] 7 8

[0131] 9 10

[0133] 11

[0135] 12

[0137] 13 14

[0139] 15 16

[0141] 17 18

[0143] 19 20

[0145] 21 22

[0147] 23 24

[0149] 25 26

[0151] 27 28

[0153] 29 30

[0155] 31 32

[0157] 33 34

[0159] 35 36

[0161] 37 38

[0163] 39 40

[0165] 41 42

[0167] 43 44

[0169] 45 46

[0171] 47 48

[0173] 49 50

[0175] 51 52

[0177] 53 54

[0179] 55 56

[0181] 57 58

[0183] 59 60

[0185] 61

[0187] 62

[0189] 63 64

[0191] 65 66

[0193] 67 68

[0195] 69 70

[0197] 71 72

[0199] 73

[0201] 74 75

[0203] 76 77

[0205] 78 79

[0207] 80

[0209] Alternatively, the photoinitiator molecule comprises one or more of the compounds, or the photoinitiator molecule consists of one or more of the compounds.

[0210] According to the invention, it may be desirable to combine two or more of the above-described embodiments with each other.

[0211] Due to the absorption of light at the second wavelength, the photoinitiator molecules may be transformed into a reactive state, thereby triggering free radical polymerization in the local volume.

[0212] The light beam of light of the first wavelength and the light beam of light of the second wavelength may be irradiated into the partial volume at least partially overlapping.

[0213] The starting material can be polymerized in a plurality of partial volumes by photopolymerization, whereby three-dimensional shaped bodies can be produced in the starting material.

[0214] In combination with an apparatus for local polymerization of the starting material, the compounds shown above can be used in combination with a method for local polymerization of the starting material by two-color photopolymerization. The same applies to methods for 3D printing of shaped bodies or methods for volumetric printing of shaped bodies.

[0215] A formulation suitable for volumetric printing may contain the following parts by weight:

[0216] - 1-99.9999% by weight, preferably 5-99.99% by weight, more preferably 20-99.9% by weight of a photopolymerizable compound, such as a monomer;

[0217] - 0-99 wt%, preferably 1-50 wt%, more preferably 3-20 wt% of the coinitiator when the coinitiator contains a photopolymerizable group such as an acrylate group;

[0218] - 0-50 wt%, preferably 1-40 wt%, more preferably 3-10 wt% of the coinitiator when the coinitiator does not contain a photopolymerizable group;

[0219] - 0.0001-20 wt %, preferably 0.001-10 wt %, more preferably 0.01-5 wt %, most preferably 0.1-1 wt % of a dual-color photoinitiator;

[0220] - 0-20% by weight, preferably 1-10% by weight, more preferably 3-5% by weight of an acid or base;

[0221] - 0-90 wt %, preferably 1-70 wt %, more preferably 5-50 wt %, most preferably 10-30 wt % of other additives, such as organic or inorganic fillers, optical brighteners, inhibitors, chain transfer agents, etc.; and

[0222] - 0-80% by weight, preferably 5-50% by weight, more preferably 10-30% by weight of solvent.

[0223] All weight ratios are given relative to the weight of the total formulation.

[0224] Typical curing parameters for volume printing can be:

[0225] - Any device that uses two different wavelengths of light;

[0226] -- Temperature from 20°C to +100°C, preferably from 0°C to +60°C, more preferably from +20°C to +60°C

[0227] - a first wavelength: 250 nm to 500 nm; preferably 300 nm to 450 nm, and

[0228] - Second wavelength: 350 nm to 800 nm.

[0229] In order to prevent the residual dual-color initiator and / or its reaction products from migrating and releasing from the cured object, the following measures are disclosed:

[0230] a) substituted in such a way that the molecular weight exceeds 1000 g / mole,

[0231] b) combining the initiator with a high molecular weight structure such as an oligomer or polymer,

[0232] c) Functionalizing the initiator with polymerizable groups that are built into the polymer network during cure, including but not limited to: acrylates, acrylamides, methacrylates, thiols + alkenes, epoxides, oxiranes, oxetanes, vinyl ethers.

[0233] Dual color initiators are disclosed for curing any resin containing molecules with functional groups polymerizable by a free radical mechanism including but not limited to acrylates, methacrylates, acrylamides, thiols+enes, and derivatives of vinyl acetate.

[0234] The disclosed dual-color photoinitiators enable volumetric printing due to their tunable thermal back reaction and their ability to initiate polymerization only when two wavelengths of light interact with the resin volume. The dual-color initiators are not limited to a specific device, but to give an illustrative example of what is required to show the thermal back reaction, the following device can be used: Volumetric printing can be performed in the following device, which consists of a light sheet generator, a projector, a container with four transparent sides and containing a resin (including at least one disclosed dual-color photoinitiator), and a movable stage for moving the container or the light sheet generator. Such a device ensures a fast curing process over the entire volume compared to the point-by-point device described by Swainson [Swainson, US4041476, US4078229, US4238840, US4466080, US4471470, US4333165]. A layer of the volume is irradiated with electromagnetic radiation of a first wavelength to switch the dual-color photoinitiator from A to B. An image is projected onto the layer from the other direction using electromagnetic radiation of a second wavelength, which causes photopolymerization, where the image and layer overlap. After a given amount of time, the electromagnetic radiation of the first wavelength moves to the adjacent layer and the next image is projected onto the layer with electromagnetic radiation of the second wavelength. In the previous layer, no further polymerization occurs due to the rapid thermal reverse reaction back to the A-form which causes the electromagnetic radiation of the second wavelength to be deactivated. After a number of iterative steps, the 3-dimensional object is solidified within the volume and can be removed, or the residual resin can be washed off. The remaining object can be post-processed.

[0235] In another aspect of the invention, a sensitizer can be used to induce switching from A to B. The sensitizer absorbs at a wavelength where both forms A and B of the dual-color initiator show minimal or no absorption. When the sensitizer is excited by electromagnetic radiation of a first wavelength, energy is transferred to the dual-color initiator in form A. The excited dual-color initiator form A is then switched to form B. B absorbs electromagnetic radiation of a second wavelength and initiates polymerization through form C. The use of a sensitizer is beneficial where the absorbance of the first wavelength changes during the irradiation process, making it possible to ensure uniform switching and curing over the entire optical path of the first wavelength. In addition, the use of a sensitizer enables the application of a higher concentration of dual-color initiator without increasing the absorbance of the first wavelength. Sensitizers also enable larger object sizes to be achieved due to more uniform curing. Typical sensitizers known in the art can be used and include, but are not limited to, derivatives of the following substances:

[0236] a) transition metal complexes, for example tris(bipyridine)ruthenium complexes, zinc porphyrin complexes, iridium complexes, rhenium complexes or platinum complexes;

[0237] b) boron dipyrromethene;

[0238] c) iodine- or bromine-substituted organic chromophores, such as Rose Bengal or Eosin B;

[0239] d) carbonyl compounds, for example naphthalene diimide, acetophenone, anthraquinone, thioxanthone, camphorquinone, benzophenone, diacetyl compounds, coumarins, benzylideneacetone, dibenzylideneacetone; and

[0240] e) Polycyclic aromatic compounds, such as anthracene, pyrene or fullerenes.

[0241] Sensitizers according to d) and e) are particularly preferred.

[0242] When a Type 2 dual-color initiator is used, the co-initiator can be selected from typical hydrogen donors or electron donors known in the art, including but not limited to derivatives of ethanolamine, aminobenzoic acid, germane, thiols, alcohols, ethers, thioethers, silanes, phosphines, acetals, dialkylanilines, N-phenylglycine, arylsulfinates or esters, iodonium salts, sulfonium salts and organic borates.

[0243] The co-initiator may have a high molecular weight, for example >1000 g / mole, or be bound to a polymer to prevent migration in the cured object. The co-initiator may contain polymerizable groups, such as acrylate / ester groups or methacrylate / ester groups, which are built into the polymer network during curing to prevent subsequent migration of the co-initiator. A typical example is as follows:

[0244]

[0245] For two-color volume printing methods, it is advantageous to control the viscosity of the resin. For type 2 initiators, a large amount of coinitiator affects the viscosity of the resin. Therefore, it is beneficial in some cases to use a coinitiator with a specific viscosity or a mixture of a common coinitiator with a low viscosity and a coinitiator with a high viscosity. Although low viscosity coinitiators are commercially available, high viscosity coinitiators are lacking.

[0246] High viscosity co-initiators consist of a portion that generates high viscosity and a portion that serves as a hydrogen donor. In order to achieve high viscosity, one structural motif relies on a backbone that geometrically cannot establish sufficient intermolecular interactions to become solid. Due to the high molecular weight, movement is restricted, resulting in high viscosity. Another structural motif is based on multiple hydrogen bonds, as in a mixture containing carbamates. In order to ensure sufficient mixing with the monomer composition on the one hand and high reactivity on the other hand, the backbone of the co-initiator can have a structure similar to that of the backbone with monomer functional groups. Therefore, it is beneficial to use a co-initiator based on a carbamate structure with a monomer composition containing a carbamate portion. It may be beneficial to use a co-initiator based on a bisphenol structure in combination with a monomer composition that also contains a bisphenol portion.

[0247] A typical structure of a highly viscous and reactive co-initiator in a bisphenol resin suitable for volume printing is as follows:

[0248] ,

[0249] Where R 28 and R 29 R 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 Can be independently selected from OH, OD, alkyl ether, aryl ether, ester or the following structure:

[0250]

[0251] Where R 30 To R 35 are independently selected from H, D, alkyl, aryl, more specifically, R 30 To R 35 R is independently selected from methyl, ethyl, ethyl-OH, (-CH2-CH2-OH) and phenyl; or 30 and R 31 , R 32 and R 33 , R 34 and R 35 It may contain atoms required for forming 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, phenoxyacetylamine, thiophene ... Phenothiazines and phenothiazines.

[0252] When the monomer composition consists of a urethane moiety, a typical structure is as follows:

[0253] ,

[0254] Where R 36 is selected from substituted or unsubstituted aryl, substituted or unsubstituted alkyl, cyclic alkyl, polyester and polyether, R 37 and R 38 R is independently selected from substituted or unsubstituted aryl, substituted or unsubstituted alkyl, cyclic alkyl, preferably -CH2-CH2-OH (ethanol), H, D, methyl, butyl, ethyl-hexyl and phenyl. 37 Can have the following structure:

[0255] ,

[0256] Where R 39 and R40 R is independently selected from substituted or unsubstituted aryl, substituted or unsubstituted alkyl, cyclic alkyl, preferably -CH2-CH2-OH (ethanol), H, D, methyl, butyl, ethyl-hexyl and phenyl. 40 Can be used with R 37 same.

[0257] The above mentioned coinitiators can be used as mixtures resulting from different degrees of functionalization. Reactivity and viscosity can be controlled by applying appropriate ratios of backbone precursors (bisphenol diglycidyl ether, bisphenol ethoxylate, diisocyanate) and amine sources, wherein the amine sources have at least two reactive functional groups, such as triethanolamine or any diethanolamine.

[0258] Suitable acids may be weak acids, such as acetic acid, formic acid, benzoic acid, or strong acids, such as trifluoroacetic acid.

[0259] 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).

[0260] Suitable solvents may be water or ethyl acetate. Formulations suitable for volumetric printing may preferably be solvent-free.

[0261] Any combination of embodiments, preferred ranges and / or parts, in particular preferred parts of the present invention is particularly preferred. BRIEF DESCRIPTION OF THE DRAWINGS

[0262] Further design examples are described below with reference to the figures in the accompanying drawings, in which

[0263] Figure 1 A schematic diagram showing an embodiment of the method according to the present invention;

[0264] Figure 2 a schematic diagram showing a method according to the present invention; and

[0265] Figure 3 Shows Figure 2 A perspective view of an embodiment of the inventive steps is shown.

[0266] Figure 1One embodiment of the present invention is schematically shown. With the aid of a first light source 10, light having a first wavelength is generated and irradiated onto a structure comprising a curable composition 14. The assembly is a layered assembly comprising a light-blocking layer 11 and two transparent layers 12. The assembly also comprises a spacer 13. In the space formed by the two transparent layers 12 and the spacer 13, a curable composition 14 corresponding to a polymerizable starting material and comprising one or more photoinitiator molecules according to the present invention is introduced. The layered structure also comprises two light-blocking layers 11, arranged so that at least a portion of the curable composition 14 can be irradiated by light of a first wavelength generated by the first light source 10 and light of a second wavelength generated by the second light source 15. The area 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.

[0267] Figure 2 and Figure 3 Another embodiment of the invention is shown, in which a portion of the curable composition 24, 34 is cured, the portion being illuminated simultaneously by both the light from the first light source 20, 30 and the light from the second light source 25, 35 through the holes 23, 33 in the light-blocking layer 21, 31, the light-blocking layer partially shielding the curable composition 24, 34 from the corresponding light sources 20, 30 and 25, 35, respectively. The curable composition 24, 34 is arranged in a transparent container 22, 32 here. In this form, it is provided that the light sources 20, 30 are arranged orthogonally with respect to the second light sources 25, 35. However, in principle, other angles are also provided here according to the invention. DETAILED DESCRIPTION

[0268] In one embodiment, a method for locally polymerizing a polymerizable starting material by two-color polymerization is provided. In two-color polymerization, a photoinitiator molecule (also referred to as a mediator molecule) absorbs photons of light of different wavelengths, thereby converting the photoinitiator molecule from an initial state through an intermediate state to a reaction state suitable for locally initiating or initiating a polymerization reaction in the polymerizable starting material, so that the starting material polymerizes until it hardens or solidifies, especially in the case of plastics.

[0269] The mediator molecule (hereinafter also referred to as photoinitiator molecule) and its necessary functions can be generated in different ways. An example is provided below:

[0270]

[0271] Photoinitiators can exist in three different states, which are characterized as follows:

[0272] Initial state (A):

[0273] - In the absence of light irradiation, the photoinitiator molecules exist in this state.

[0274] Intermediate state (B):

[0275] The -B state is the electronic ground state.

[0276] - An intermediate state is generated from the initial state A by absorbing light of wavelength λ1.

[0277] -The photoinitiator molecules have a new or more intense absorption band for light of wavelength λ2.

[0278] - Alternatively, the absorption band of λ1 disappears. The photoinitiator molecules spontaneously return to the initial state A in the absence of light or by absorbing light of wavelength λ3.

[0279] Reaction state (C):

[0280] -By absorbing light of wavelength λ2, a reactive state is generated from the intermediate state B.

[0281] -Reactive state initiates polymerization in the immediate vicinity of the molecule.

[0282] - The reverse reaction from A to B is not desired.

[0283] Example

[0284] The following describes the functions and effects of the present invention in detail through specific embodiments of the present invention. However, the embodiments provided are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

[0285] synthesis

[0286] Numbering scheme for spiropyrans

[0287]

[0288] Spiropyran, Spiropyran General synthesis of oxazine, spiroimidazole, quinoline, indole, benzothiazole (compounds 1-10, 13-21, 28, 29, 31-57, 62, 64, 70, 77, 78)

[0289] Indolene (1 mmol) or benzothiazole precursor (1 mmol) was dissolved in ethanol (5 mL). Salt or benzothiazole In the case of salt, salt (1 mmol) and piperidine (1.5 mmol) were dissolved in ethanol (5 mL) and stirred for 15 minutes. Salicylaldehyde (1 mmol) or o-nitrosophenol (1 mmol) or 1H-benzo[d]imidazole-4-carboxaldehyde (1 mmol) were added and the mixture was heated to 70°C until the starting material was exhausted. After cooling to room temperature, the product precipitated or water was added to precipitate the product. The solid was filtered and washed with ethanol or water. When the filtering procedure did not produce pure product, the aqueous mixture was extracted with dichloromethane. The combined organic layers were dried over anhydrous MgSO4 and the solvent was evaporated under reduced pressure. The solid residue was purified by recrystallization from ethanol or silica gel column chromatography using acetone / petroleum ether mixture as eluent.

[0290] 1

[0292] 1 H NMR (500 MHz, chloroform-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). C 30 H 25 FNO2 + ESI-MS [M+H] + m / z calculated: 450.186, found: 450.197.

[0293] 2

[0295] 1H NMR (500 MHz, chloroform-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 = 8.2Hz, 1H), 5.75 (d, J = 10.3 Hz, 1H), 2.82 (s, 3H), 1.32 (s, 3H), 1.19 (s, 3H). C 27 H 22 FN2O2 + ESI-MS [M+H] + m / z calculated: 425.166, found: 425.172.

[0296] 3

[0298] 1 H NMR (500 MHz, chloroform-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). C 26 H 24 NO2 + ESI-MS [M+H] + m / z calculated: 382.180, found: 382.190.

[0299] 4

[0301] 1 H NMR (500 MHz, chloroform-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 = 8.6Hz, 1H), 5.92 (d, J = 10.3 Hz, 1H), 2.83 (s, 3H), 1.36 (s, 3H), 1.22 (s, 3H). C 26 H 23 N2O4 + ESI-MS [M+H] + m / z calculated: 427.165, found: 427.173.

[0302] 5

[0304] 1 H NMR (500 MHz, chloroform-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 = 8.8Hz, 1H), 5.87 (d, J = 10.3 Hz, 1H), 2.84 (s, 3H), 1.34 (s, 3H), 1.22 (s, 3H). C 26 H 23 N2O4 + ESI-MS [M+H] + m / z calculated: 427.165, measured: 427.172.

[0305] 6

[0307] 1H NMR (500 MHz, chloroform-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, 0.7Hz, 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). C 32 H 28 NO2 + ESI-MS [M+H] + m / z calculated: 458.212, measured: 458.223.

[0308] 7

[0310] 1 H NMR (500 MHz, dichloromethane-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).

[0311] C 26 H 23 FNO2 + ESI-MS [M+H] + m / z calculated: 400.171, found: 400.175.

[0312] 8

[0314] 1 H NMR (500 MHz, dichloromethane-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). C 31 H 25 FNO2 + ESI-MS [M+H] + m / z calculated: 462.186, found: 462.190.

[0315] 9

[0317] 1 H NMR (500 MHz, chloroform-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).

[0318] C26 H 23 N2O4 + ESI-MS [M+H] + m / z calculated: 427.165, found: 427.155.

[0319] 10

[0321] 1 H NMR (500 MHz, dichloromethane-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), 5.86 (d, J = 10.2 Hz, 1H),2.86 (s, 3H), 1.37 (s, 3H), 1.22 (s, 3H).

[0322] C 33 H 28 NO3 + ESI-MS [M+H] + m / z calculated: 486.206, found: 486.199.

[0323] 13

[0325] 1H NMR (500 MHz, dichloromethane-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).

[0326] C 29 H 27 N2O4 + ESI-MS [M+H] + m / z calculated: 467.197, found: 467.215.

[0327] 14

[0329] 1 H NMR (500 MHz, dichloromethane-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).

[0330] C 35 H 32 NO5 + ESI-MS [M+H] + m / z calculated: 546.227, found: 546.236.

[0331] 15

[0333] 1 H NMR (500 MHz, toluene-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, 0.7Hz, 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).

[0334] C 26 H 22 FINO2 + ESI-MS [M+H] + m / z calculated: 526.369, found: 526.354.

[0335] 16

[0337] 1 H NMR (500 MHz, chloroform-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).

[0338] C 27 H22 F4NO2 + ESI-MS [M+H] + m / z calculated: 468.158, found: 468.150.

[0339] 17

[0341] 1 H NMR (500 MHz, chloroform-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 = 10.3Hz, 1H), 4.55 – 4.46 (m, 1H), 4.16 (d, J = 16.5 Hz, 1H), 1.33 (s, 3H), 1.26 (s, 3H).

[0342] C 32 H 28 NO2 + ESI-MS [M+H] + m / z calculated: 458.211, found: 458.223.

[0343] 18

[0345] 1H NMR (500 MHz, chloroform-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).

[0346] C 27 H 25 FNO4S + ESI-MS [M+H] + m / z calculated: 478.148, found: 478.122.

[0347] 19

[0349] 1 H NMR (400 MHz, chloroform-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).

[0350] C 26 H 24 FN2O4S + ESI-MS [M+H] + m / z calculated: 479.144, found: 479.163.

[0351] 20

[0353] 1 H NMR (400 MHz, dichloromethane-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).

[0354] C 26 H 24 NO3 + ESI-MS [M+H] + m / z calculated: 398.175, found: 398.189.

[0355] twenty one

[0357] 1 H NMR (500 MHz, dichloromethane-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, 1.0 Hz, 1H), 1H), 2.86 (s, 3H), 1.29 (s, 3H), 1.11 (s, 3H).

[0358] C 26 H24 NO4 + ESI-MS [M+H] + m / z calculated: 414.170, found: 414.161.

[0359] 28

[0361] 1 H NMR (500 MHz, chloroform-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).

[0362] C 30 H 29 F3NO4 + ESI-MS [M+H] + m / z calculated: 524.204, found: 524.216.

[0363] 29

[0365] 1H NMR (400 MHz, chloroform-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).

[0366] C 29 H 27 F3NO3 + ESI-MS [M+H] + m / z calculated: 494.194, found: 494.181.

[0367] 31

[0369] 1 H NMR (400 MHz, chloroform-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).

[0370] C 23 H 21 F3NO4 + ESI-MS [M+H] + m / z calculated: 432.142, found: 432.151.

[0371] 32

[0373] 1 H NMR (500 MHz, chloroform-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).

[0374] C 26 H 24 NO2 + ESI-MS [M+H] + m / z calculated: 382.180, found: 382.162.

[0375] 33

[0377] 1 H NMR (500 MHz, chloroform-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).

[0378] C 26 H 24 NO2 + ESI-MS [M+H] + m / z calculated: 382.180, found: 382.184.

[0379] 34

[0381] 1 H NMR (500 MHz, benzene-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, 1.4Hz, 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 = 7.7Hz, 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).

[0382] C 27 H 24 NO3 + ESI-MS [M+H] + m / z calculated: 410.175, found: 410.188.

[0383] 35

[0385] 1H NMR (500 MHz, chloroform-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, 1.6Hz, 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).

[0386] C 26 H 23 N2O4 + ESI-MS [M+H] + m / z calculated: 427.165, found: 427.154.

[0387] 36

[0389] 1 H NMR (400 MHz, chloroform-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).

[0390] C 27 H 26 NO3 + ESI-MS [M+H] + m / z calculated: 412.191, found: 412.184.

[0391] 37

[0393] 1 H NMR (500 MHz, chloroform-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).

[0394] C 30 H 26 NO2 + ESI-MS [M+H] + m / z calculated: 432.196, measured: 432.201.

[0395] 38

[0397] 1 H NMR (500 MHz, CHLOROFORM-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).

[0398] C 27 H 26 NO3 + ESI-MS [M+H] + m / z calculated: 412.191, found: 412.184.

[0399] 39

[0401] 1 H NMR (500 MHz, chloroform-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).

[0402] C 30 H 26 NO2 + ESI-MS [M+H] + m / z calculated: 432.196, measured: 432.203.

[0403] 40

[0405] 1 H NMR (500 MHz, dichloromethane-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).

[0406] C 26 H 23 INO2 + ESI-MS [M+H] + m / z calculated: 508.077, found: 508.069.

[0407] 41

[0409] 1 H NMR (500 MHz, dichloromethane-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).

[0410] C 26 H 22 I2NO2 + ESI-MS [M+H] + m / z calculated: 633.973, measured: 633.971.

[0411] 42

[0413] 1 H NMR (500 MHz, dichloromethane-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).

[0414] C 27 H 24 N3O + ESI-MS [M+H] + m / z calculated: 406.191, found: 406.202.

[0415] 43

[0417] 1 H NMR (500 MHz, CHLOROFORM-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).

[0418] C 29 H 25 N2O2 + ESI-MS [M+H] + m / z calculated: 433.191, found: 433.196.

[0419] 44

[0421] 1 H NMR (500 MHz, dichloromethane-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).

[0422] C 25 H 23 N2O2 + ESI-MS [M+H] + m / z calculated: 383.175, found: 383.169.

[0423] 45

[0425] 1H NMR (400 MHz, CHLOROFORM-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).

[0426] C 27 H 23 F3O + ESI-MS [M+H] + m / z calculated: 424.182, found: 424.199.

[0427] 46

[0429] 1 H NMR (500 MHz, CHLOROFORM-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).

[0430] C 31 H 27 N2O4 + ESI-MS [M+H] + m / z calculated: 491.197, found: 491.192.

[0431] 47

[0433] 1H NMR (500 MHz, CHLOROFORM-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).

[0434] C 30 H 33 N2O2 + ESI-MS [M+H] + m / z calculated: 453.254, found: 453.256.

[0435] 48

[0437] 1 H NMR (500 MHz, chloroform-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, 2.4Hz, 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).

[0438] C 28 H 27 N2O4 + ESI-MS [M+H] + m / z calculated: 455.197, found: 455.185.

[0439] 49

[0441] 1 H NMR (500 MHz, chloroform-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).

[0442] C 30 H 31 FNO2 + ESI-MS [M+H] + m / z calculated: 456.233, measured: 456.240

[0443] 50

[0445] 1 H NMR (500 MHz, benzene-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 = 10.2Hz, 1H), 2.51 (s, 3H), 1.24 (s, 3H), 0.96 (s, 3H).

[0446] C 26 H 23 FNO2 + ESI-MS [M+H] +m / z calculated: 400.171, found: 400.175.

[0447] 51

[0449] 1 H NMR (500 MHz, toluene-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 = 10.3Hz, 1H), 2.44 (s, 3H), 1.13 (m, J = 2.1 Hz, 12H), 0.93 (s, 3H).

[0450] C 31 H 31 NO3 + ESI-MS [M+H] + m / z calculated: 465.230, found: 465.241.

[0451] 52

[0453] 1 H NMR (500 MHz, chloroform-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).

[0454] C 26 H 22 F2NO2 + ESI-MS [M+H] + m / z calculated: 418.161, found: 418.169.

[0455] 53

[0457] 1 H NMR (500 MHz, CHLOROFORM-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).

[0458] C 27 H 24 IN2O5 + ESI-MS [M+H] + m / z calculated: 583.072, found: 583.084.

[0459] 54

[0461] 1 H NMR (500 MHz, chloroform-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).

[0462] C27 H 25 N2O5 + ESI-MS [M+H] + m / z calculated: 457.176, found: 457.168.

[0463] 55

[0465] 1 H NMR (500 MHz, CHLOROFORM-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).

[0466] C 27 H 25 N2O5 + ESI-MS [M+H] + m / z calculated: 457.176, found: 457.165.

[0467] 56

[0469] 1 H NMR (500 MHz, chloroform-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 = 8.2Hz, 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).

[0470] C 30 H 31 BrNO2 + ESI-MS [M+H] + m / z calculated: 516.153, found: 516.171.

[0471] 57

[0473] 1 H NMR (500 MHz, chloroform-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, 0.9Hz, 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).

[0474] C 28 H 28 NO2 + ESI-MS [M+H] + m / z calculated: 410.211, found: 410.222.

[0475] 62

[0477] 1H NMR (400 MHz, chloroform-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).

[0478] C 41 H 35 N4O3 + ESI-MS [M+H] + m / z calculated: 631.270, found: 631.284.

[0479] 64

[0481] 1 H NMR (500 MHz, dichloromethane-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, 1.4Hz, 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).

[0482] C 25 H 31 N2O2 + ESI-MS [M+H] + m / z calculated: 391.238, found: 391.230.

[0483] 70

[0485] 1 H NMR (500 MHz, chloroform-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, 1.7Hz, 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).

[0486] C 27 H 26 NO3 + ESI-MS [M+H] + m / z calculated: 412.508, found: 412.499.

[0487] 77

[0489] 1 H NMR (500 MHz, acetonitrile-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).

[0490] C 31 H 35 N2O2 + ESI-MS [M] + m / z calculated: 467.269, found: 467.278.

[0491] 78

[0493] 1 H NMR (500 MHz, dichloromethane-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).

[0494] C 24 H 20 NO2S + ESI-MS [M+H] + m / z calculated: 386.121, found: 386.125.

[0495] Synthesis of Compounds 10-12

[0496] The corresponding acid chloride derivative (15 mmol) and unsubstituted spiropyran (5 mmol) or 8'-methoxyspiropyran (5 mmol) were dissolved in dichloromethane (50 mL) and cooled to 0°C. AlCl3 (17 mmol) was added in small portions over 1 hour. The resulting mixture was stirred at room temperature for 2 hours. The mixture was poured onto ice (200 g) and extracted with dichloromethane. The combined organic layers were dried over anhydrous MgSO4 and the solvent was evaporated under reduced pressure. The solid residue was purified by recrystallization from ethanol or by silica gel column chromatography using an acetone / petroleum ether mixture as eluent.

[0497] 11

[0499] 1H NMR (500 MHz, dichloromethane-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).

[0500] C 34 H 30 NO4 + ESI-MS [M+H] + m / z calculated: 516.217, found: 516.210.

[0501] 12

[0503] 1 H NMR (500 MHz, dichloromethane-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).

[0504] C 35 H 32 NO5 + ESI-MS [M+H] + m / z calculated: 546.227, found: 546.218.

[0505] Synthesis of compounds 22, 25, 64, and 68

[0506] 6'-bromospiropyran (3 mmol) was dissolved in anhydrous tetrahydrofuran (15 mL) and cooled to -78 ° C. n-Butyl lithium (3.1 mmol) was added dropwise and the solution was stirred for 30 minutes. The corresponding nitrile derivative (5 mmol) was added over 15 minutes and the reaction was warmed to room temperature. Stirring was continued at room temperature for 2 hours, then water was added and the reaction mixture was extracted with dichloromethane. The combined organic layers were dried over anhydrous MgSO4 and the solvent was evaporated under reduced pressure. The solid residue was purified by silica gel column chromatography using recrystallization from ethanol or an acetone / petroleum ether mixture as an eluent.

[0507] twenty two

[0509] 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).

[0510] C 24 H 28 NO2 + ESI-MS [M+H] + m / z calculated: 362.211, found: 362.219.

[0511] 25

[0513] 1H NMR (500 MHz, chloroform-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 = 8.5Hz, 1H), 2.99 (s, 3H), 1.30 (s, 3H), 1.25 (s, 6H), 1.14 (s, 3H), 0.12 (s, 9H).

[0514] C 26 H 34 NO3Si + ESI-MS [M+H] + m / z calculated: 436.230, found: 436.238.

[0515] 68

[0517] 1 H NMR (500 MHz, chloroform-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).

[0518] C 29 H 38 NO3Si + ESI-MS [M+H] + m / z calculated: 476.262, found: 476.269.

[0519] Synthesis of Compounds 23 and 24

[0520] 2-mercaptobenzoic acid (0.5 mmol) or phthalic anhydride (0.5 mmol) is slowly dissolved in sulfuric acid (1mL) and stirred for 15 minutes. 5-trifluoromethyl spiropyran (0.5 mmol) is slowly added in 30 minutes and continues to stir for 2 hours. Add ice (10 g) and use Na2CO3 aqueous solution (10%) to neutralize the mixture. The reaction mixture is extracted with ethyl acetate. The organic layer merged is through anhydrous MgSO4 and the solvent is evaporated under reduced pressure. Residue is purified by silica gel column chromatography using ethyl acetate / petroleum ether mixture as eluent.

[0521] twenty three

[0523] 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).

[0524] C 27 H 21 F3NO2S + ESI-MS [M+H] + m / z calculated: 480.124, found: 480.116.

[0525] twenty four

[0527] 1H 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).

[0528] C 28 H 21 F3NO3 + ESI-MS [M+H] + m / z calculated: 476.147, found: 476.152.

[0529] Synthesis of compound 26

[0530] Compound 25 (3 mmoles) is dissolved in tetrahydrofuran, tetrabutylammonium fluoride (1 M in THF, 4.5 mmoles) is added. The mixture is stirred for 1 hour and extracted with ethyl acetate. The combined organic layer is 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 ethyl acetate / petroleum ether mixture as eluent. The obtained alcohol is dissolved in acetonitrile. Iodomethane (6 mmoles) and Cs2CO3 (6 mmoles) are added and the mixture is heated to 70 ° C overnight. After cooling to room temperature, water is added, and the mixture is extracted with ethyl acetate. The combined organic layer is 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 mixture as eluent.

[0531] 26

[0533] 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).

[0534] C 24 H 27 NO3 + ESI-MS [M+H] + m / z calculated: 378.206, found: 378.219.

[0535] Synthesis of compound 27

[0536] 2-Bromo-2-methylpropanoyl bromide (5.25 mmol) was dissolved in dichloromethane (50 mL) and cooled to 0°C. AlCl3 (5.5 mmol) was added in small portions and stirring was continued for 15 minutes. 5-Trifluoromethyl spiropyran (5 mmol) was added over 30 minutes and stirring was continued for 2 hours. The reaction solution was poured over ice (50 g) and extracted with dichloromethane. The combined organic layers were dried over anhydrous MgSO4 and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using ethyl acetate / petroleum ether mixture as eluent.

[0537] The α-bromobutyrate (2 mmol) obtained is dissolved in acetonitrile (25 mL) and sodium toluenesulfinate (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 layer is dried over anhydrous MgSO4 and the solvent is evaporated under reduced pressure. Residue is purified by silica gel column chromatography using acetone / petroleum ether mixture as eluent.

[0538] 27

[0540] 1H 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).

[0541] C 30 H 32 NO4S + ESI-MS [M+H] + m / z calculated: 502.205, found: 502.216.

[0542] Synthesis of compound 30

[0543] 2,2,2-Trichloroacetyl chloride (2.1 mmol) was dissolved in dichloromethane (20 mL) and cooled to 0°C. AlCl3 (2.2 mmol) was added in small portions and stirring was continued for 15 minutes. 5-trifluoromethyl spiropyran (2 mmol) was added over 30 minutes and stirring was continued for 2 hours. The reaction was poured onto ice (20 g) and extracted with dichloromethane. The combined organic layers were dried over anhydrous MgSO4 and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using an ethyl acetate / petroleum ether mixture as eluent.

[0544] 30

[0546] 1H 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).

[0547] C 22 H 18 Cl3F3NO2 + ESI-MS [M+H] + m / z calculated: 490.035, found: 490.180.

[0548] Synthesis of Compounds 58-60 and 63

[0549] 5-Trifluoromethyl spiropyran (5 mmol), MgCl2 (7.5 mmol), triethylamine (18.75 mmol) and paraformaldehyde (33.75 mmol) were dissolved in THF and heated to 70 ° C for 3 days. The mixture was cooled to room temperature, neutralized with 1 M HCl aqueous solution, and extracted with ethyl acetate. The combined organic layer was dried over anhydrous MgSO4 and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using ethyl acetate / petroleum ether mixture as eluent. The reaction was carried out in the same manner using 5-trifluoromethyl-5',7'-dimethyl spiropyran, 5-trifluoromethyl-5',7'-dimethoxy spiropyran or 5-trifluoromethyl-6',7'-difluoro-N-(3,5-dimethylbenzyl)-spiropyran.

[0550] Under argon atmosphere, 5-trifluoromethyl-6'-formyl spiropyran (2.5 mmoles) and diphenylphosphine oxide (2.5 mmoles) are dissolved in THF (25 mL). Triethylamine (2.5 mmoles) is added dropwise and stirring is continued for 18 hours. Water is added and the mixture is extracted with ethyl acetate. The combined organic layer is dried over anhydrous MgSO4 and the solvent is evaporated under reduced pressure. Residue is purified by silica gel column chromatography using ethyl acetate / petroleum ether mixture as eluent. Use 5-trifluoromethyl-5', 7'-dimethyl-6'-formyl spiropyran, 5-trifluoromethyl-5', 7'-dimethoxy-6'formyl spiropyran or 5-trifluoromethyl-6', 7'-difluoro-N-(3,5-dimethyl-4-formylbenzyl)-spiropyran to react in the same manner.

[0551] The corresponding formyl spiropyran derivative (1.5 mmol) and MnO2 (30 mmol) were mixed in dichloromethane and stirred overnight. The reaction solution was filtered through celite and the solvent was evaporated under reduced pressure. Silica gel column chromatography was performed using ethyl acetate / petroleum ether mixture as eluent to produce the desired product.

[0552] 58

[0554] 1 H NMR (400 MHz, chloroform-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).

[0555] C 33 H 28 F3NO3P + ESI-MS [M+H] + m / z calculated: 574.175, found: 574.189.

[0556] 59

[0558] 1 H NMR (400 MHz, chloroform-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).

[0559] C 35 H 32 F3NO3P + ESI-MS [M+H] + m / z calculated: 602.207, found: 602.199.

[0560] 60

[0562] 1 H NMR (400 MHz, chloroform-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).

[0563] C 35 H 32 F3NO5P + ESI-MS [M+H] + m / z calculated: 634.196, measured: 634.182.

[0564] 63

[0566] 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 = 8.5 Hz, 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).

[0567] C 41 H 34 F5NO3P + ESI-MS [M+H] + m / z calculated: 714.219, found: 714.211.

[0568] Synthesis of compound 61

[0569] 5-Trifluoromethyl-6'-formylspiropyran (5 mmol) and 1,3-propanedithiol (5 mmol) were dissolved in chloroform (10 mL) and cooled to -10°C. Gaseous HCl was passed through the solution for 45 minutes and stirring was continued at 0°C for 30 minutes and at room temperature overnight. The solvent was evaporated under reduced pressure and the residue was suspended in methanol (5 mL). The slurry was stirred overnight and filtered. The solid residue was dried under reduced pressure.

[0570] Under argon atmosphere, dithiane derivative (5 mmol) was dissolved in anhydrous tetrahydrofuran (10 mL) and cooled to -78°C. n-Butyl lithium (1.6 M in hexane, 5 mmol) was added dropwise. The solution was warmed to 0°C and stirred for 30 minutes. Anhydrous tetrahydrofuran (5 mL) containing diethyl germanium dichloride (2 mmol) was added dropwise, and stirred at 0°C for 3 hours and continued to stir at room temperature overnight. Water was added and the mixture was extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous MgSO4. The solvent was removed under reduced pressure. Ethyl acetate (2.5 mL) was added to the solid residue to obtain a suspension. After stirring overnight, methanol (5 mL) was added and continued to stir for 24 hours. The suspension was filtered, washed with ethyl acetate / methanol (1 / 1), and dried under reduced pressure.

[0571] Dithiane diethylgermanium derivative (1.5 mmoles) is dissolved in tetrahydrofuran (10 mL) and water (2 mL) is added. Accompanied by intermittent ice cooling, CaCO (1.8 mmoles) and iodine (1.8 mmoles) are added in multiple portions over 4 hours. The reaction mixture is stirred at room temperature overnight and filtered through silica gel. Saturated sodium dithionite aqueous solution is added until the color of the resulting suspension becomes yellow. Filter the mixture and wash with water. Residue is dissolved in ethyl acetate and washed with water. The organic phase is dried over anhydrous MgSO and the solvent is evaporated under reduced pressure. Use ethyl acetate / petroleum ether as eluent to carry out silica gel column chromatography to produce the desired product.

[0572] 61

[0574] 1 H 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).

[0575] C 46 H 45 F6GeN2O4 + ESI-MS [M+H] +m / z calculated: 877.249, found: 877.221.

[0576] Synthesis of compound 65

[0577] 2-Bromo-2-methylpropanoyl bromide (5.25 mmol) was dissolved in dichloromethane (50 mL) and cooled to 0°C. AlCl3 (5.5 mmol) was added in small portions and stirring was continued for 15 minutes. 5-Trifluoromethyl spiropyran (5 mmol) was added over 30 minutes and stirring was continued for 2 hours. The reaction solution was poured over ice (50 g) and extracted with dichloromethane. The combined organic layers were dried over anhydrous MgSO4 and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using ethyl acetate / petroleum ether mixture as eluent.

[0578] The α-bromobutyrate (2 mmol) obtained was dissolved in morpholine (10 mL) and heated to 80 ° C for 2 days. After cooling to room temperature, water was added, and the mixture was extracted with ethyl acetate. The combined organic layer was dried over anhydrous MgSO4 and the solvent was evaporated under reduced pressure. Residue was purified by silica gel column chromatography using acetone / petroleum ether mixture as eluent.

[0579] Alternatively, the α-bromobutyrate (2 mmoles) obtained is dissolved in toluene (2 mL) and added dropwise to a methanol solution of sodium methoxide (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 to 130°C for 24 hours. After cooling to room temperature, water is added and the mixture is extracted with ethyl acetate. The combined organic layer is dried over anhydrous MgSO4 and the solvent is evaporated under reduced pressure. Residue is purified by silica gel column chromatography using an acetone / petroleum ether mixture as eluent.

[0580] 65

[0582] 1H NMR (400 MHz, chloroform-d) 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).

[0583] C 28 H 32 F3N2O3 + ESI-MS [M+H] + m / z calculated: 501.236, found: 501.240.

[0584] Synthesis of compounds 66 and 67

[0585] 2-Bromobutyryl bromide (5.25 mmol) was dissolved in dichloromethane (50 mL) and cooled to 0°C. AlCl3 (5.5 mmol) was added in small portions and stirring was continued for 15 minutes. 5-Trifluoromethyl spiropyran (5 mmol) was added over 30 minutes and stirring was continued for 2 hours. The reaction solution was poured onto ice (50 g) and extracted with dichloromethane. The combined organic layers were dried over anhydrous MgSO4 and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using an ethyl acetate / petroleum ether mixture as eluent.

[0586] The resulting α-bromobutyrate (2 mmol) was dissolved in tetrahydrofuran and added dropwise to a solution of the corresponding amine in tetrahydrofuran (2 M, 10 mmol) at 0° C. The mixture was stirred at 0° C. for 2 hours and at room temperature for another 4 hours. The solvent was evaporated under reduced pressure to give the α-aminobutyrate which was used directly in the next step.

[0587] The α-aminobutyric acid ester (2 mmol) obtained is dissolved in acetonitrile (10 mL), benzyl bromide (2.5 mmol) and heated to 70 ℃ 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). An aqueous solution of NaOH (30%, 10 mL) is added, and the mixture is heated to 60 ℃ for 4 hours. After cooling to room temperature, the mixture is neutralized with 1 M HCl aqueous solution and extracted with ethyl acetate. The combined organic layer is 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 eluent.

[0588] 66

[0590] 1 H NMR (500 MHz, chloroform-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).

[0591] C 33 H 36 F3N2O2 + ESI-MS [M+H] + m / z calculated: 549.272, found: 549.284.

[0592] 67

[0594] 1H NMR (400 MHz, chloroform-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).

[0595] C 35 H 38 F3N2O3 + ESI-MS [M+H] + m / z calculated: 591.283, measured: 591.288.

[0596] Synthesis of compound 69

[0597] Compound 68 (3 mmol) was dissolved in tetrahydrofuran and tetrabutylammonium fluoride (1 M in THF, 4.5 mmol) was added. The mixture was stirred for 1 hour and extracted with ethyl acetate. The combined organic layer was washed with water and dried over anhydrous MgSO4. The solvent was evaporated under reduced pressure and the residue was purified by silica gel column chromatography using ethyl acetate / petroleum ether mixture as eluent.

[0598] 69

[0600] 1H 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), 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).

[0601] C 26 H 30 NO3 + ESI-MS [M+H] + m / z calculated: 404.222, found: 404.228.

[0602] Synthesis of Compounds 71-74

[0603] Compound 70 (2 mmol) was dissolved in anhydrous dichloromethane (5 mL) and the corresponding isocyanate was added dropwise. The reaction mixture was stirred for 1 hour and the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography using acetone / petroleum ether mixture or methanol / dichloromethane mixture as eluent.

[0604] 71

[0606] 1H 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 = 4.2Hz, 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 = 0.9Hz, 3H), 1.29 (s, 3H), 1.15 (s, 3H).

[0607] C 34 H 35 N2O6 + ESI-MS [M+H] + m / z calculated: 567.249, found: 567.241.

[0608] 72

[0610] 1H NMR (500 MHz, chloroform-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).

[0611] C 33 H 33 N2O6 + ESI-MS [M+H] + m / z calculated: 553.233, found: 553.245.

[0612] 73

[0614] 1H NMR (500 MHz, chloroform-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).

[0615] C 174 H 270 N6O 45 2+ ESI-MS [M+2H] 2+ m / z calculated: 1582.452, measured: 1582.436.

[0616] 74

[0618] 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).

[0619] Synthesis of compounds 75 and 76

[0620] Compound 70 (3 mmol) was dissolved in acetonitrile (25 mL) and cooled to 0°C. Tosyl chloride (10 mmol) or 2-bromomethyl-1,4-benzodione was added. In 40mL argon ether (10 mmoles) and KCO (11 mmoles), and the mixture was heated to 70 ℃ and continued for 2 days. The reaction mixture was stirred for 1 hour and the solvent was removed under reduced pressure. The silica gel column chromatography using acetone / petroleum ether mixture or methanol / dichloromethane mixture as eluent was used to purify the residue. Add water, and extract the mixture with ethyl acetate. The organic layer merged is through anhydrous MgSO4 dry and evaporated under reduced pressure solvent. The silica gel column chromatography using acetone / petroleum ether mixture as eluent was used to purify the residue.

[0621] 75

[0623] 1H NMR (500 MHz, chloroform-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, 1.1Hz, 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).

[0624] C 35 H 32 NO5 + ESI-MS [M+H] + m / z calculated: 546.227, found: 546.239.

[0625] 76

[0627] 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).

[0628] C 34 H 32 NO5S + ESI-MS [M+H] + m / z calculated: 566.200, found: 566.208.

[0629] Synthesis of compounds 79 and 80

[0630] 4-Hydroxybenzophenone (4 mmol), corresponding 1,1-diaryl-2-propyn-1-ol (4 mmol) and β-cyclodextrin hydrate (320 mg) were dissolved in water (10 mL) and heated to 90 ° C overnight. The mixture was extracted with ethyl acetate. The combined organic layer was dried over anhydrous MgSO4 and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography using an acetone / petroleum ether mixture as eluent.

[0631] 79

[0633] 1H NMR (500 MHz, chloroform-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, 0.7Hz, 1H), 6.17 (d, J = 9.9 Hz, 1H), 3.80 (s, 6H).

[0634] C 30 H 25 O4 + ESI-MS [M+H] + m / z calculated: 449.175, found: 449.184.

[0635] 80

[0637] 1 H NMR (500 MHz, chloroform-d) δ 9.49 (d, J = 8.0 Hz, 1H), 9.33 (d, J = 8.2Hz, 1H), 7.42 – 7.30 (m, 4H), 7.28 (d, J = 4.1 Hz, 3H), 7.24 – 7.17 (m, 3.83 – 3.71 (m, 4H), 3.21– 3.12 (m, 4H).

[0638] C 32 H 28 NO3 + ESI-MS [M+H] + m / z calculated: 474.206, found: 474.220.

[0639] Synthesis of precursors

[0640]

[0641] 1-Hydroxy-1-carbonitrile cyclohexane (10 g) was dissolved in THF (50 mL), cooled to -20 °C, and then Et3N (13 mL) was added. A solution of trimethylchlorosilane (12 g in 20 mL THF) was added dropwise. The solution was stirred at -20 °C for 1.5 hours and stirred overnight at room temperature. The mixture was extracted with methyl tert-butyl ether, and the combined organic layers were dried over anhydrous MgSO4. The solvent was evaporated under reduced pressure, and the product was obtained as a transparent liquid after distillation.

[0642] 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).

[0643]

[0644] 2-Hydroxy-2-carbonitrile propane (25 g) was dissolved in THF (150 mL), cooled to -20 °C, and then Et3N (46 mL) was added. A solution of trimethylchlorosilane (42 g in 65 mL THF) was added dropwise. The solution was stirred at -20 °C for 1.5 hours and stirred overnight at room temperature. The mixture was extracted with methyl tert-butyl ether, and the combined organic layers were dried over anhydrous MgSO4. The solvent was evaporated under reduced pressure, and the product was obtained as a transparent liquid after distillation.

[0645] 1 H NMR (500 MHz, CHLOROFORM-d) δ 1.58 (s, 6H), 0.22 (s, 9H).

[0646] General Synthesis of Salicylaldehyde

[0647] The corresponding phenol derivative (5 mmoles) and NaOH (105 mmoles) are dissolved in water (55 mL) and heated to 70 ℃ to 90 ℃. Chloroform (75 mmoles) is added and heating is continued until the starting material is consumed. When the reaction is not completed and stops, other chloroform (75 mmoles) is added. After being cooled to room temperature, the mixture is acidified with aqueous hydrochloric acid solution (10%) and extracted with methyl tertiary butyl ether. The organic layer merged is mixed with water (100 mL) and KOH (7.5 g). The water layer is washed with chloroform and then acidified with aqueous hydrochloric acid solution (10%). The aqueous phase is extracted with methyl tertiary butyl ether, and the organic extract from the merging of the last step is dried through anhydrous MgSO4. The solvent is removed under reduced pressure, and products therefrom is directly used in the next step without further purification.

[0648] Synthesis of o-nitrosophenol

[0649] The corresponding phenol (25 mmol) was dissolved in acetic acid (150 mL) and water (17 mL) containing NaNO2 (75 mmol) was added dropwise at 0°C. The mixture was stirred at 0°C for 2 hours and at room temperature for another 4 hours. Water was added to precipitate the crude product, which was filtered off and used without further purification.

[0650] Indole General synthesis of salt

[0651] The corresponding aniline derivative (50 mmol) was dissolved in a mixture of concentrated aqueous hydrochloric acid solution (20 mL) and ice water (30 mL). Water containing NaNO2 (100 mmol) was added at 0°C. After stirring for 30 minutes, a concentrated aqueous hydrochloric acid solution (35 mL) containing SnCl2 (28.4 g) was added. The resulting mixture was stirred for 30 minutes, filtered, and washed with water or 1M aqueous hydrochloric acid solution to obtain hydrazine hydrochloride, which was used directly in the next step.

[0652] The corresponding hydrazine (as hydrochloride) (47.5 mmoles), 3-methyl butan-2-ketone and concentrated sulfuric acid aqueous solution are dissolved in glacial acetic acid (68 mL). The mixture is refluxed for 24 hours, and the main part of acetic acid is then distilled out. After being cooled to room temperature, the residue is neutralized with saturated NaHCO aqueous solution. The mixture is extracted with dichloromethane, and the organic phase merged is dried over anhydrous MgSO, followed by solvent evaporation under reduced pressure. If the purity of indole is not enough for the next step, petroleum ether / ethyl acetate mixture is used to carry out silica gel column chromatography as eluent.

[0653] The obtained indole (30 mmol) was dissolved in acetonitrile (150 mL) and the corresponding alkyl halide (60 mmol) was added. The mixture was refluxed for 24 hours. After cooling to room temperature, the product precipitated, filtered and washed with acetonitrile. When the product did not precipitate, the solvent was evaporated under reduced pressure. The indole was purified by recrystallization from acetonitrile or acetone.

[0654]

[0655] 1 H NMR (500 MHz, DMSO-d6) δ 7.43 (s, 1H), 7.24 (m, 2H), 4.03 (m, 6H), 0.85 (s, 6H).

[0656] C 13 H 15 N2 + ESI-MS [M] + m / z calculated: 199.123, found: 199.129.

[0657]

[0658] 1 H NMR (500 MHz, acetonitrile-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). C 12 H 15 N2O2 + ESI-MS [M] + m / z calculated: 219.113, found: 219.119.

[0659]

[0660] 1H 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).

[0661] C 19 H 20 NO + ESI-MS [M] + m / z calculated: 278.154, found: 278.158.

[0662]

[0663] 1 H 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).

[0664] C 19 H 19 FNO + ESI-MS [M] + m / z calculated: 296.145, found: 296.155.

[0665]

[0666] 1H NMR (500 MHz, chloroform-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, 0.9Hz, 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).

[0667] C 21 H 24 NO + ESI-MS [M] + m / z calculated: 306.185, found: 306.181.

[0668] Synthesis of Coinitiator

[0669] Example 1

[0670] Bisphenol A diglycidyl ether (10 g, 29.4 mmol) is added to triethanolamine (26.3 g, 176 mmol) and the mixture is stirred at room temperature overnight. The mixture is dissolved in acetone / methanol (25 / 1) and filtered through silica gel. The solvent is removed under reduced pressure to obtain a viscous oily product. Other amines can be used instead of triethanolamine, for example morpholine, dicyclohexylamine or dimethylamine.

[0671] Example 2

[0672] 2-Isocyanatoethyl acrylate (1 g, 7.1 mmol) was 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 hour, dichloromethane was added and the mixture was washed with water. After evaporation of the solvent under reduced pressure, a viscous oily product was obtained. The procedure can be applied to other ethanolamine derivatives and 2-isocyanatoethyl methacrylate.

[0673] Composition of an exemplary formulation:

[0674] Example Preparation 1

[0675] 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). The mixture was stirred until homogenous and could be used directly for printing.

[0676] Example Formulation 2

[0677] Initiator 2 (2 mg) was dissolved in ethyl acetate (0.5 g) and added to a mixture of triethanolamine (1 g) and diurethane dimethacrylate isomer mixture, CAS 72869-86-4 (10 g). The mixture was stirred until homogenous and was directly ready for printing.

[0678] Example Preparation 3

[0679] Initiator 2 (2 mg) was dissolved in ethyl acetate (0.5 g) and added to a mixture of triethanolamine (1 g), bisphenol A glycerol (1 glycerol / phenol) diacrylate (5 g) and pentaerythritol tetraacrylate (5 g). The mixture was stirred until homogenized and was ready for printing.

[0680] Example Preparation 4

[0681] 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). The mixture was stirred until homogenous and could be used directly for printing.

[0682] Example Preparation 5

[0683] 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). The mixture was stirred until homogenous and could be used directly for printing.

[0684] Example Preparation 6

[0685] Initiator 65 (100 mg) and 2-isopropylthioxanthone (100 mg) were dissolved in ethyl acetate (2 g) and added to pentaerythritol tetraacrylate (10 g). The mixture was stirred until homogenous and can be used directly for printing.

[0686] Example Formulation 7

[0687] Initiator 66 (100 mg) and 2-isopropylthioxanthone (100 mg) were dissolved in ethyl acetate (2 g) and added to pentaerythritol tetraacrylate (10 g). The mixture was stirred until homogenous and can be used directly for printing.

[0688] Example Preparation 8

[0689] Initiator 28 (100 mg) and 2-isopropylthioxanthone (100 mg) were dissolved in ethyl acetate (2 g) and added to pentaerythritol tetraacrylate (10 g). The mixture was stirred until homogenous and can be used directly for printing.

[0690] Example Preparation 9

[0691] Initiator 2 (2 mg) was dissolved in ethyl acetate (0.5 g) and added to a mixture of viscous co-initiator (Example 2, 1 g) and diurethane dimethacrylate isomer mixture, CAS 72869-86-4 (10 g). The mixture was stirred until homogenous and can be used directly for printing.

[0692] Example Formulation 10

[0693] Initiator 65 (2 mg) was dissolved in ethyl acetate (0.5 g) and added to pentaerythritol tetraacrylate (10 g). The mixture was stirred until homogenous and can be used directly for printing.

[0694] Example Preparation 11

[0695] Initiator 66 (2 mg) was dissolved in isobornyl acrylate (1 g) and added to diurethane dimethacrylate isomer mixture, CAS 72869-86-4 (10 g). The mixture was stirred until homogenous and can be used directly for printing.

[0696] Example Formulation 12

[0697] 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% in water, 10 g). The mixture was stirred until homogenized and was directly ready for printing.

[0698] The above formulation is used for volumetric printing in an apparatus in which a cuvette with four transparent windows is illuminated with a light sheet of wavelength 1 in one direction, while an image is projected onto the light sheet at wavelength 2 from another angle. When the cuvette or the light sheet moving through the cuvette is moved, the image is changed to produce a movie. Printing results in curing only in the volume where the two wavelengths of light intersect. The residual uncured resin is removed and a formed body is obtained, which is further washed with a solvent and post-cured. Specifically, the following conditions are used for the given example formulation:

[0699] Wavelength 1: 375 nm, Wavelength 2: 565 nm, Temperature 5°C, 25°C or 45°C:

[0700] Preparations 1-5 and 9-12

[0701] Wavelength 1: 405 nm, Wavelength 2: 565 nm, Temperature 25°C:

[0702] Preparations 6, 7, and 8

[0703] Xolographic experiment Figure 1-3 )

[0704] 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 irradiated by two LEDs with luminescence peaks of about 375 nm and 617 nm, respectively. The irradiation of the two LEDs was partially blocked by an opaque layer. The opaque layer can be changed during irradiation, for example, in terms of their position. The material hardened at a point in time when the two beams irradiated the sample long enough. After the irradiation was completed, the sample was washed with EtOH to obtain a solid three-dimensional body.

[0705] The features disclosed in the above description, the claims and the drawings may be relevant to the implementation of various designs either alone or in any combination.

Claims

1. A method for locally polymerizing a starting material by two-color photopolymerization, the method include: - providing a polymerizable starting material comprising photoinitiator molecules which can be transformed by sequential photoexcitation into a reactive state in which they locally trigger polymerization of the starting material; and - photopolymerizing the starting material in the local volume by irradiating light of a first wavelength and light of a second wavelength different from the first wavelength into the local volume, thereby - the photoinitiator molecules change from an initial state in which the photoinitiator molecules do not substantially absorb light of the second wavelength to an intermediate state having changed optical properties compared to the initial state due to the absorption of light of the first wavelength, such that the photoinitiator molecules in the intermediate state absorb light of the second wavelength; as well as - the photoinitiator molecules are converted from the intermediate state to the reactive state due to the absorption of light of the second wavelength, thereby locally triggering the polymerization, Wherein the light of the first wavelength and the light of the second wavelength intersect where the image is projected on the light sheet.

2. The method according to claim 1, wherein - the polymerizable starting material is arranged in a container having transparent sides; - light of said first wavelength is irradiated into the layer of said local volume by means of a light sheet generator; and - The container, the light sheet generator or both are moved during photopolymerization.

3. The method according to claim 1 or 2, Features The light of the first wavelength and the light of the second wavelength are simultaneously irradiated into the local volume.

4. The method according to any one of claims 1 to 3, It is characterized in that The intermediate state is the electronic ground state.

5. The method according to at least one of the preceding claims, Features The photoinitiator molecules in the intermediate state do not substantially absorb light of the first wavelength.

6. The method according to at least one of the preceding claims, Features The photoinitiator molecules in the volume where polymerization is not desired are transformed from the intermediate state to the initial state due to absorption of light of a third wavelength.

7. The method according to at least one of the preceding claims, Features The photoinitiator molecules are transformed into a reactive state due to absorption of light at the second wavelength, which triggers free radical polymerization in the local volume.

8. The method according to at least one of the preceding claims, Features The polymeric starting material further comprises a co-initiator and / or a sensitizer.

9. The method according to at least one of the preceding claims, Features The polymerizable starting material may also contain additives, acids and / or bases.

10. The method according to at least one of the preceding claims, Features The beam of light of the first wavelength and the beam of light of the second wavelength intersect where an image is projected on the light sheet.

11. The method according to at least one of the preceding claims, Features The starting material is polymerized by photopolymerization in a plurality of partial volumes and thus a three-dimensional shaped body is produced in the starting material.

12. The method according to at least one of the preceding claims, Features The intermediate state can be higher than k=0.01s at the printing temperature. -1 The rate constant for thermal return to the initial state.

13. The method according to at least one of the preceding claims, Features The first wavelength is 250-500 nm; the second wavelength is 350-800 nm.

14. The method according to at least one of the preceding claims, Features The polymerization is carried out at a temperature ranging from -20°C to 100°C.

15. The method according to at least one of the preceding claims, Features The method comprises the following sub-steps: - performing a first irradiation on a first layer of the partial volume using light of a first wavelength, wherein the partial volume is divided into n layers, the first irradiation causing the photoinitiator molecules in the first layer to be transformed from an initial state to an intermediate state; - first projecting a first image onto the first layer from a different direction using light of a second wavelength, thereby inducing polymerization where the first image and the first layer overlap; - performing a second irradiation on the second layer of the partial volume using light of the first wavelength, wherein the second irradiation causes the photoinitiator molecules in the second layer to be converted from an initial state to an intermediate state; - a second projection of a second image onto the second layer from a different direction using light of a second wavelength, thereby inducing polymerization where the second image and the second layer overlap; - Repeat the above two steps for the third to nth layers using the third to nth images, thereby obtaining a three-dimensional object.

16. The method of claim 15, wherein the first irradiation and first projection steps are performed before the second irradiation and second projection, and each repetition is performed after the preceding irradiation and projection steps.

17. A method according to claim 15 or 16, wherein the method comprises the further sub-step of post-processing the three-dimensional object.

18. An apparatus for locally polymerizing a starting material by two-color photopolymerization, the apparatus comprising: - inlet for polymerizable starting materials; - a light generating unit arranged to generate light of a first wavelength and light of a second wavelength, the second wavelength being different from the first wavelength; - a light guiding device arranged to illuminate light of said first wavelength and light of said second wavelength into the local volume; - a projector arranged to project an image onto the layer of said partial volume; and - movable table; in - the inlet comprises a container having transparent sides, wherein the interior of the container comprises the partial volume; - said light generating unit for generating light of a first wavelength comprises a light sheet generator arranged to irradiate light of the first wavelength into the layer of said partial volume; - the movable stage is arranged to move the container, the light sheet generator or both; The device is suitable for performing the following procedures: - introducing, through the inlet, the polymerizable starting material, the starting material comprising photoinitiator molecules, which can be excited by sequential photoexcitation into a reactive state in which the photoinitiator molecules locally initiate polymerization of the starting material; as well as - photopolymerizing the starting material in the local volume by irradiating the local volume with light of the first wavelength and light of the second wavelength, thereby - the photoinitiator molecules change from an initial state in which the photoinitiator molecules do not substantially absorb light of the second wavelength to an intermediate state having changed optical properties compared to the initial state due to the absorption of light of the first wavelength, such that the photoinitiator molecules in the intermediate state absorb light of the second wavelength; as well as - the photoinitiator molecules are converted from the intermediate state to the reactive state due to the absorption of light of the second wavelength, thereby locally triggering the polymerization.

19. The apparatus according to claim 18, wherein the device is further adapted to perform the operation The following sub-steps of the sequence: - irradiating a first layer of the partial volume with light of a first wavelength, wherein the partial volume is divided into n layers, the irradiation causing the photoinitiator molecules in the first layer to be transformed from an initial state to an intermediate state; - projecting a first image onto the first layer from a different direction using light of a second wavelength, thereby inducing polymerization where the first image and the first layer overlap; - irradiating the second layer of the partial volume with light of a first wavelength, the irradiation causing the photoinitiator molecules in the second layer to be converted from an initial state to an intermediate state; - projecting a second image onto the second layer from a different direction using light of a second wavelength, thereby inducing polymerization where the second image and the second layer overlap; - Repeat the above two steps for the third to nth layers using the third to nth images, thereby obtaining a three-dimensional object.

Images