Photoacid molecules based on dihalogenated methyl o-nitroaromatic compounds and their applications

Abstract

The present invention provides photoacid molecules based on dihalogenated methyl o-nitro aromatic compounds and their applications, belonging to the field of photosensitive molecules. The present invention provides the application of dihalogenated methyl o-nitro aromatic compounds or dipseudohalogenated methyl o-nitro aromatic compounds as photoacid molecules. The dihalogenated methyl o-nitro aromatic compounds or dipseudohalogenated methyl o-nitro aromatic compounds produce acidic products under light: light causes the dihalogenated methyl o-nitro aromatic compounds or dipseudohalogenated methyl o-nitro aromatic compounds to rearrange their structures, generating unstable intermediates that decompose to produce the acid corresponding to the halogen or pseudohalogen.

Description

Technical Field

[0001] The present invention relates to the field of photosensitive molecules, and in particular to photoacid molecules based on dihalogenated methyl o-nitro aromatic compounds and applications thereof. Background Art

[0002] Photoacids, also known as photoacid generators, are a special class of photosensitive molecules that undergo molecular structural changes upon exposure to light, producing acidic products. Due to their unique photochemical properties, photoacids are used in a wide range of fields, particularly as a core component of chemically amplified photoresists. In photoresists, the acidic products produced by photoacids upon exposure to light act as catalysts, catalyzing the cleavage of acid-sensitive groups on the resin's side chains. This drastically alters the resin's polarity or solubility in certain solvents, thereby enabling pattern transfer.

[0003] Dihalogenated methyl o-nitroaromatic compounds have been reported before, but they have not been used as photoacid molecules. For example, dichloromethyl o-nitrobenzene is used as an intermediate in the synthesis of anticancer active molecules. Summary of the Invention

[0004] The present invention provides a photoacid molecule based on a dihalogenated methyl o-nitro aromatic compound and application thereof. The dihalogenated methyl o-nitro aromatic compound or the di-pseudo-halogenated methyl o-nitro aromatic compound can generate acid.

[0005] The present invention provides the application of a dihalogenated methyl o-nitro aromatic compound or a dipseudo-halogenated methyl o-nitro aromatic compound as a photoacid molecule.

[0006] Preferably, the halogen in the dihalomethyl o-nitroaromatic compound includes one or more of F, Cl, Br and I;

[0007] The number of dihalogenated methyl groups and nitro groups in the dihalogenated methyl o-nitro aromatic compound is ≥1;

[0008] The pseudo-halogen in the di-pseudo-halogenated methyl o-nitro aromatic compound includes one or more of thiocyanate, selenocyanate, oxycyanate and cyanate;

[0009] The number of dipseudohalogenated methyl groups and nitro groups in the dipseudohalogenated methyl o-nitro aromatic compound is both ≥1.

[0010] Preferably, the aromatic group in the dihalogenated methyl o-nitro aromatic compound includes one or more of phenyl, naphthyl, anthracenyl and aromatic heterocyclic groups;

[0011] The aromatic heterocyclic group includes furyl and / or indolyl.

[0012] Preferably, the dihalomethyl o-nitroaromatic compound comprises a polymer;

[0013] The structural unit of the polymer includes an aromatic group, a dihalogenated methyl group located on the benzene ring of the aromatic group, and a nitro group located at the ortho position of the dihalogenated methyl group.

[0014] Preferably, the dihalogenated methyl o-nitro aromatic compound has a structural formula shown in any one of Formulas I to V:

[0015]

[0016] Preferably, the dihalogenated methyl o-nitro aromatic compound or the dipseudo-halogenated methyl o-nitro aromatic compound and the non-basic compound are used simultaneously;

[0017] The non-basic compound can undergo a substitution reaction with a carbonyl halide group or a carbonyl pseudohalogen to generate an acid corresponding to the halogen or an acid corresponding to the pseudohalogen.

[0018] Preferably, the non-basic compound includes one or more of alcohol, water, phenol and thiol.

[0019] Preferably, the dihalogenated methyl o-nitro aromatic compound or the dipseudohalogenated methyl o-nitro aromatic compound is used as a photoacid molecule in the removal of trityl protection.

[0020] The present invention also provides a photoresist, characterized in that it comprises a dihalogenated methyl o-nitro aromatic compound and / or a dipseudo-halogenated methyl o-nitro aromatic compound, an organic solvent and a resin containing an acid-sensitive group.

[0021] The present invention also provides a photoresist, characterized in that it comprises a dihalogenated methyl o-nitro aromatic compound and / or a dipseudohalogenated methyl o-nitro aromatic compound, an organic solvent, a non-alkaline compound and a resin containing an acid-sensitive group;

[0022] The non-basic compound can undergo a substitution reaction with a carbonyl halide group or a carbonyl pseudohalogen to generate an acid corresponding to the halogen or an acid corresponding to the pseudohalogen.

[0023] The dihalogenated methyl o-nitro aromatic compound or the dipseudo-halogenated methyl o-nitro aromatic compound produces an acidic product under light: light causes the structure of the dihalogenated methyl o-nitro aromatic compound or the dipseudo-halogenated methyl o-nitro aromatic compound to rearrange, generating an unstable intermediate, which decomposes to produce an acid corresponding to the halogen or an acid corresponding to the pseudo-halogen.

[0024] The dihalogenated methyl o-nitro aromatic compound or the dipseudohalogenated methyl o-nitro aromatic compound decomposes under light to produce the acid corresponding to the halogen or the acid corresponding to the pseudohalogen, while releasing a highly reactive intermediate containing a carbonyl halide group or a carbonyl pseudohalogen. The intermediate further reacts with a non-alkaline compound to produce a second molecule of the acid corresponding to the halogen or the acid corresponding to the pseudohalogen. Therefore, compared to o-nitrobenzyl-based photosensitizers that can only produce one acid molecule, the dihalogenated methyl o-nitro aromatic compound or the dipseudohalogenated methyl o-nitro aromatic compound of the present invention can produce two acid molecules, with high acid production efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 For Example 1 1 H-NMR monitoring results;

[0026] Figure 2 This is the result of ultraviolet spectrum monitoring of the photochemical reaction in Example 1. DETAILED DESCRIPTION

[0027] The present invention provides the application of a dihalogenated methyl o-nitro aromatic compound or a dipseudo-halogenated methyl o-nitro aromatic compound as a photoacid molecule.

[0028] In the present invention, the dihalomethyl o-nitro aromatic compound or dipseudohalogenated methyl o-nitro aromatic compound refers to a dihalomethyl or dipseudohalogenated methyl, nitro-substituted H of the benzene ring in the aromatic group, and the dihalomethyl or dipseudohalogenated methyl is located in the ortho position of the nitro group. When it contains multiple dihalomethyl or dipseudohalogenated methyl and nitro groups, one dihalomethyl or dipseudohalogenated methyl and one nitro group is used as a unit, and the dihalomethyl or dipseudohalogenated methyl is located in the ortho position of the nitro group, which means that the dihalomethyl or dipseudohalogenated methyl in the unit is located in the ortho position of the nitro group.

[0029] The dihalogenated methyl o-nitro aromatic compound or the dipseudohalogenated methyl o-nitro aromatic compound is preferably used as a photoacid molecule in the removal of trityl protection, and the object of the trityl protection removal preferably includes trityl-protected propylene glycol monomethyl ether.

[0030] In the present invention, the aromatic group in the dihalogenated methyl o-nitro aromatic compound or the dipseudohalogenated methyl o-nitro aromatic compound includes one or more of phenyl, naphthyl, anthracenyl and aromatic heterocyclic groups; the aromatic heterocyclic group preferably includes furyl and / or indolyl.

[0031] In the present invention, the number of dihalomethyl and nitro groups in the dihalomethyl o-nitro aromatic compound is preferably ≥1. In a specific embodiment of the present invention, the number of dihalomethyl and nitro groups in the dihalomethyl o-nitro aromatic compound can both be 1 or 2; the halogen in the dihalomethyl o-nitro aromatic compound includes one or more of F, Cl, Br and I.

[0032] In the present invention, the number of dipseudohalogenated methyl groups and nitro groups in the dipseudohalogenated methyl o-nitro aromatic compound is preferably ≥1. In a specific embodiment of the present invention, the number of dipseudohalogenated methyl groups and nitro groups in the dipseudohalogenated methyl o-nitro aromatic compound can be 1 or 2; the pseudohalogen in the dipseudohalogenated methyl o-nitro aromatic compound includes one or more of thiocyanate, selenocyanate, oxycyanate and cyanate.

[0033] In the present invention, the dihalogenated methyl o-nitro aromatic compound includes a polymer;

[0034] The structural unit of the polymer includes an aromatic group, a dihalogenated methyl group located on the benzene ring of the aromatic group, and a nitro group located at the ortho position of the dihalogenated methyl group.

[0035] In the present invention, the dihalogenated methyl o-nitro aromatic compound preferably has a structural formula shown in any one of Formulas I to V:

[0036]

[0037] In the present invention, the dihalogenated methyl o-nitro aromatic compound or the dipseudohalogenated methyl o-nitro aromatic compound is preferably used simultaneously with a non-basic compound that reacts with an acyl chloride.

[0038] In the present invention, the non-alkaline compound preferably includes one or more of alcohol, water, phenol and thiol; the alcohol preferably includes methanol; the non-alkaline compound can undergo a substitution reaction with a carbonyl halide group or a carbonyl pseudohalogen to generate an acid corresponding to the halogen or an acid corresponding to the pseudohalogen.

[0039] The present invention also provides a photoresist comprising a dihalogenated methyl o-nitro aromatic compound and / or a dipseudohalogenated methyl o-nitro aromatic compound, an organic solvent and a resin containing an acid-sensitive group.

[0040] The present invention also provides a photoresist comprising a dihalogenated methyl o-nitro aromatic compound and / or a dipseudohalogenated methyl o-nitro aromatic compound, an organic solvent, a non-alkaline compound and a resin containing an acid-sensitive group;

[0041] The non-basic compound can undergo a substitution reaction with a carbonyl halide group or a carbonyl pseudohalogen to generate an acid corresponding to the halogen or an acid corresponding to the pseudohalogen.

[0042] In the present invention, the solvent preferably includes one or more of chloroform, tetrahydrofuran and dioxane.

[0043] The photoacid molecules based on dihalogenated methyl o-nitro aromatic compounds and their applications provided by the present invention are described in detail below with reference to the examples, but they should not be construed as limiting the scope of protection of the present invention.

[0044] Example 1

[0045] Step 1: Add 10 mmol of o-nitrobenzaldehyde to 10 mL of thionyl chloride, then add 0.5 mL of DMF. React at 80°C for 2 h. Remove excess thionyl chloride by rotary evaporation. Separate the product using a basic alumina column with a 1 / 10 petroleum ether / ethyl acetate solvent to obtain dichloromethyl o-nitrobenzene.

[0046]

[0047] Step 2: Dissolve dichloromethyl o-nitrobenzene in a mixed solvent of deuterated methanol and deuterated chloroform with a volume ratio of 1:1 (concentration 10 mg / mL), 1 H-NMR was used to monitor the changes in the molecule after 255nm UV irradiation for different time periods, and UV spectroscopy was used to monitor the changes in the photochemical reaction process (the final concentration of dichloromethyl o-nitrobenzene was 0.01 mg / mL). Figure 1 for 1 H-NMR monitoring results; Figure 2 The results of photochemical reactions were monitored by UV spectroscopy.

[0048] Depend on Figures 1-2 It can be seen that the reaction process is as follows:

[0049]

[0050] Example 2

[0051] Step 1: Synthesis: Dissolve 10 mmol of o-nitrotoluene and 20 mmol of N-bromosuccinimide in tetrachloromethane and react at 80°C under nitrogen for 6 hours. Remove the solvent by rotary evaporation, and then separate the product using a basic alumina column with a 1 / 10 petroleum ether / ethyl acetate solvent to obtain dibromomethyl o-nitrobenzene.

[0052]

[0053] Step 2: Application, demonstration of trityl removal: Dissolve 5 mol of dibromomethyl o-nitrobenzene and 10 mol of trityl-protected propylene glycol monomethyl ether in 100 mL of a mixed solvent of methanol and tetrahydrofuran (volume ratio 1:4). Irradiate with 255 nm UV light and monitor the reaction using a TLC plate until the product spots completely disappear. The monitoring results indicate that the reaction process is as follows:

[0054]

[0055] Example 3

[0056] Step 1: Synthesis: Add 10 mmol of o-nitrobenzaldehyde to 10 mL of thionyl chloride and 0.5 mL of DMF. React at 80°C for 2 h. Remove excess thionyl chloride by rotary evaporation. Then separate the product using a basic alumina column with a 1 / 10 petroleum ether / ethyl acetate solvent to obtain dichloromethyl o-nitrobenzene.

[0057] Step 2: Dissolve dichloromethyl o-nitrobenzene in a mixed solvent of water and dioxane at a volume ratio of 1:1 (concentration 10 mg / mL), and monitor the changes in the above process by ultraviolet spectroscopy (the final concentration of dichloromethyl o-nitrobenzene is 0.01 mg / mL). According to the monitoring results, the reaction process is as follows:

[0058]

[0059] Example 4

[0060] Step 1, synthesis: 4-methyl-3-nitronaphthalene (10 mmol) and N-bromosuccinimide (20 mmol) were dissolved in tetrachloromethane, heated at 80 ° C for 4 h, and the solvent was removed by rotary evaporation. Then, the mixture was separated by basic alumina chromatography column with petroleum ether / ethyl acetate (1 / 10) as the eluent.

[0061] Step 2: Photoacid detection: the photoacid product was dissolved in a mixed solvent of deuterated methanol and deuterated chloroform with a volume ratio of 1:1 (concentration 10 mg / mL). 1 H-NMR monitors the changes in the molecules after 255nm UV irradiation for different times. According to the monitoring results, the reaction process is as follows:

[0062]

[0063] Example 5

[0064] Step 1, synthesis: 2,5-dinitro-p-xylene (10 mmol) and N-bromosuccinimide (20 mmol) were dissolved in tetrachloromethane, heated at 80 ° C for 4 h, and the solvent was removed by rotary evaporation. Then, the mixture was separated by basic alumina chromatography column with petroleum ether / ethyl acetate (1 / 10) as the eluent.

[0065]

[0066] Step 2: Photoacid detection: the photoacid product was dissolved in a mixed solvent of deuterated methanol and deuterated chloroform with a volume ratio of 1:1 (concentration 10 mg / mL). 1 H-NMR monitors the changes in the molecules after 255nm UV irradiation for different times. According to the monitoring results, the reaction process is as follows:

[0067]

[0068] Example 6

[0069] Step 1: Dissolve 4-methyl-3-nitro-styrene (10 mmol) and N-bromosuccinimide (20 mmol) in tetrachloromethane, heat at 80°C for 4 h, remove the solvent by rotary evaporation, and then separate using a basic alumina column with petroleum ether / ethyl acetate (1 / 10) as the eluent.

[0070]

[0071] Step 2: Dissolve 1 mmol of the product, 4-dibromomethyl-3-nitro-styrene, and 50 mmol of Boc-protected 4-hydroxystyrene in 100 mL of dioxane. Add 0.1 mmol of azobisbutyronitrile, bubble nitrogen through the mixture for 20 minutes, seal, and heat at 70°C for 12 hours. Add the reaction mixture dropwise to petroleum ether, separate the solid, dissolve it in dioxane, and precipitate it with petroleum ether. Repeat three times and dry.

[0072] Step 3: The sample was dissolved in a mixed solvent of dioxane and methanol at a volume ratio of 1:1 (concentration 10 mg / mL), irradiated at 255 nm, and characterized by gel permeation chromatography for molecular weight changes. The reaction process was as follows:

[0073]

[0074] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. Application of dihalogenated methyl o-nitroaromatic compounds or dipseudohalogenated methyl o-nitroaromatic compounds as photoacid molecules.

2. The use according to claim 1, characterized in that The halogen in the dihalogenated methyl o-nitro aromatic compound includes one or more of F, Cl, Br and I; The number of dihalogenated methyl groups and nitro groups in the dihalogenated methyl o-nitro aromatic compound is ≥1; The pseudo-halogen in the di-pseudo-halogenated methyl o-nitro aromatic compound includes one or more of thiocyanate, selenocyanate, oxycyanate and cyanate; The number of dipseudohalogenated methyl groups and nitro groups in the dipseudohalogenated methyl o-nitro aromatic compound is both ≥1.

3. The use according to claim 1, characterized in that The aromatic group in the dihalogenated methyl o-nitro aromatic compound includes one or more of phenyl, naphthyl, anthracenyl and aromatic heterocyclic groups; The aromatic heterocyclic group includes furyl and / or indolyl.

4. The use according to claim 1, characterized in that The dihalogenated methyl o-nitro aromatic compound includes a polymer; The structural unit of the polymer includes an aromatic group, a dihalogenated methyl group located on the benzene ring of the aromatic group, and a nitro group located at the ortho position of the dihalogenated methyl group.

5. The use according to any one of claims 1 to 4, characterized in that: The dihalogenated methyl o-nitro aromatic compound has a structural formula shown in any one of Formulas I to V:

6. The use according to any one of claims 1 to 4, characterized in that: The dihalogenated methyl o-nitro aromatic compound or the dipseudo-halogenated methyl o-nitro aromatic compound and the non-basic compound are used simultaneously; The non-basic compound can undergo a substitution reaction with a carbonyl halide group or a carbonyl pseudohalogen to generate an acid corresponding to the halogen or an acid corresponding to the pseudohalogen.

7. The use according to claim 6, characterized in that The non-basic compound includes one or more of alcohol, water, phenol and thiol.

8. The use according to claim 1, characterized in that The dihalogenated methyl o-nitro aromatic compound or the dipseudo-halogenated methyl o-nitro aromatic compound is used as a photoacid molecule in removing trityl protection.

9. A photoresist, characterized in that The invention comprises a dihalogenated methyl o-nitro aromatic compound and / or a dipseudo-halogenated methyl o-nitro aromatic compound, an organic solvent and a resin containing an acid-sensitive group.

10. A photoresist, characterized in that: It comprises a dihalogenated methyl o-nitro aromatic compound and / or a dipseudo-halogenated methyl o-nitro aromatic compound, an organic solvent, a non-alkaline compound and a resin containing an acid-sensitive group; The non-basic compound can undergo a substitution reaction with a carbonyl halide group or a carbonyl pseudohalogen to generate an acid corresponding to the halogen or an acid corresponding to the pseudohalogen.

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