Photoacid molecule based on dihalogenated methyl o-nitro aromatic compound and application thereof

Abstract

The invention provides a photoacid molecule based on a dihalogenated methyl o-nitro aromatic compound and application thereof, and belongs to the field of photosensitive molecules. The invention provides an application of a dihalogenated methyl o-nitro aromatic compound or a di-pseudo-halogenated methyl o-nitro aromatic compound as a photoacid molecule. The preparation method comprises the following steps: generating an acidic product from a dihalogenated methyl o-nitro aromatic compound or a di-pseudo-halogenated methyl o-nitro aromatic compound under illumination; rearranging the structure of the dihalogenated methyl o-nitro aromatic compound or the di-pseudo-halogenated methyl o-nitro aromatic compound due to illumination to generate an unstable intermediate; and decomposing to generate acid corresponding to halogen or acid corresponding to pseudo-halogen.

Description

Technical Field

[0001] The 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] Photoacid molecules, also known as photoacid generators, are a special type of photosensitive molecules that undergo molecular structural changes under light and produce acidic products. Due to their unique photochemical properties, photoacid molecules can be used in many fields, especially as the core component of chemically amplified photoresists. In photoresists, the acidic products produced by photoacid molecules under light can act as catalysts to catalyze the acid-sensitive groups on the side chains of the resin, causing the side chains to break, resulting in a huge change in the polarity of the resin or its solubility in certain solvents, thereby achieving pattern transfer.

[0003] Dihalomethyl 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 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 invention provides application of dihalogenated methyl o-nitro aromatic compounds or dipseudo-halogenated methyl o-nitro aromatic compounds as photoacid molecules.

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

[0007] The number of dihalomethyl groups and nitro groups in the dihalomethyl 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 di-pseudo-halogenated methyl groups and the number of nitro groups in the di-pseudo-halogenated methyl o-nitro aromatic compound are 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 a furyl group and / or an indolyl group.

[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 a benzene ring in the aromatic group, and a nitro group located at an ortho position of the dihalogenated methyl group.

[0014] Preferably, the dihalomethyl 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 di-pseudo-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 dipseudo-halogenated 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 di-pseudo-halogenated 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] Dihalogenated methyl o-nitro aromatic compounds or dipseudo-halogenated methyl o-nitro aromatic compounds produce acidic products under light: light causes the dihalogenated methyl o-nitro aromatic compounds or dipseudo-halogenated methyl o-nitro aromatic compounds to rearrange their structures, produce unstable intermediates, and decompose to produce the acid corresponding to the halogen or the acid corresponding to the pseudo-halogen.

[0024] The dihalogenated methyl o-nitro aromatic compound or the dipseudo-halogenated methyl o-nitro aromatic compound decomposes under light to produce an acid corresponding to the halogen or an acid corresponding to the pseudo-halogen, while releasing a highly active intermediate containing a carbonyl halide group or a carbonyl pseudo-halogen, and the intermediate further reacts with a non-alkaline compound to produce a second molecule of an acid corresponding to the halogen or an acid corresponding to the pseudo-halogen. Therefore, compared to the o-nitrobenzyl-type photosensitive component that can only produce one acid molecule, the dihalogenated methyl o-nitro aromatic compound or the dipseudo-halogenated methyl o-nitro aromatic compound of the present invention can produce two acid molecules, and the acid production efficiency is high. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

[0027] The invention provides application of dihalogenated methyl o-nitro aromatic compounds or dipseudo-halogenated methyl o-nitro aromatic compounds as photoacid molecules.

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

[0029] The dihalogenated methyl o-nitro aromatic compound or the di-pseudo-halogenated 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 group; the aromatic heterocyclic group preferably includes furanyl 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 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 comprises a polymer;

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

[0035] In the present invention, the dihalomethyl 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 di-pseudo-halogenated 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 di-pseudo-halogenated 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 in conjunction with the embodiments, 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, add 0.5 mL of DMF, and react at 80°C for 2 h. Remove the excess thionyl chloride by rotary evaporation, and then separate using a basic alumina column with petroleum ether / ethyl acetate (1 / 10) as the eluent to obtain dichloromethyl o-nitrobenzene.

[0046]

[0047] Step 2: Dissolve dichloromethyl o-nitrobenzene in a mixed solvent of deuterated methanol and deuterated chloroform in a volume ratio of 1:1 (concentration 10 mg / mL), 1 H-NMR monitors the changes in the molecule after 255nm ultraviolet light exposure for different time periods, and ultraviolet spectroscopy is used to monitor the changes in the photochemical reaction process (the final concentration of dichloromethyl o-nitrobenzene is 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: 10 mmol of o-nitrotoluene and 20 mmol of N-bromosuccinimide were dissolved in tetrachloromethane and reacted at 80°C for 6 hours under nitrogen protection. The solvent was removed by rotary evaporation, and then separated by a basic alumina column with petroleum ether / ethyl acetate (1 / 10) as the eluent to obtain dibromomethyl o-nitrobenzene.

[0052]

[0053] Step 2: Application, demonstration of removal of trityl protection: 5 mol of dibromomethyl o-nitrobenzene and 10 mol of trityl-protected propylene glycol monomethyl ether were dissolved in 100 mL of a mixed solvent of methanol and tetrahydrofuran in a volume ratio of 1:4, and illuminated with 255 nm ultraviolet light. The reaction process was monitored with a TLC spot plate until the product spot completely disappeared. According to the monitoring results, the reaction process was as follows:

[0054]

[0055] Example 3

[0056] Step 1: Synthesis, add 10 mmol of o-nitrobenzaldehyde to 10 mL of thionyl chloride, add 0.5 mL of DMF, and react at 80°C for 2 h. Remove the excess thionyl chloride by rotary evaporation, and then separate using a basic alumina column with petroleum ether / ethyl acetate (1 / 10) as the eluent to obtain dichloromethyl o-nitrobenzene.

[0057] Step 2: Dissolve dichloromethyl o-nitrobenzene in a mixed solvent with a volume ratio of water to dioxane 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, the solvent was removed by rotary evaporation, and then separated by basic alumina chromatography column, the eluent was petroleum ether / ethyl acetate (1 / 10).

[0061] Step 2: Photoacid detection: Dissolve the photoacid product in a mixed solvent of deuterated methanol and deuterated chloroform with a volume ratio of 1:1 (concentration 10 mg / mL) and 1 H-NMR monitors the changes in molecules after 255nm ultraviolet light exposure 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, the solvent was removed by rotary evaporation, and then separated by a basic alumina column, the eluent being petroleum ether / ethyl acetate (1 / 10).

[0065]

[0066] Step 2: Photoacid detection: Dissolve the photoacid product in a mixed solvent of deuterated methanol and deuterated chloroform with a volume ratio of 1:1 (concentration 10 mg / mL) and 1 H-NMR monitors the changes in molecules after 255nm ultraviolet light exposure 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 for 20 min, seal, and heat at 70°C for 12 h. Drop the reaction liquid into petroleum ether, separate the solid, dissolve it in dioxane, precipitate it with petroleum ether, repeat three times, and dry.

[0072] Step 3: Dissolve the sample in a mixed solvent of dioxane and methanol in a volume ratio of 1:1 (concentration 10 mg / mL), irradiate with 255 nm light, and characterize the molecular weight change by gel permeation chromatography. According to the characterization results, the reaction process is 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 principle of the present invention. These improvements and modifications should also be regarded as 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 dihalomethyl groups and nitro groups in the dihalomethyl 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 di-pseudo-halogenated methyl groups and the number of nitro groups in the di-pseudo-halogenated methyl o-nitro aromatic compound are 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 a furyl group and / or an indolyl group.

4. The use according to claim 1, characterized in that: The dihalomethyl o-nitroaromatic compound includes a polymer; The structural unit of the polymer includes an aromatic group, a dihalogenated methyl group located on a benzene ring in the aromatic group, and a nitro group located at an 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 di-pseudo-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 di-pseudo-halogenated methyl o-nitro aromatic compound is used as a photoacid molecule in the removal of trityl protection.

9. A photoresist, characterized in that: The invention comprises a dihalogenated methyl o-nitro aromatic compound and / or a di-pseudo-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 di-pseudo-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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