CN108084028B - Preparation method of molecular glass photoresist containing bisphenol A framework structure - Google Patents
Preparation method of molecular glass photoresist containing bisphenol A framework structure Download PDFInfo
- Publication number
- CN108084028B CN108084028B CN201611046954.1A CN201611046954A CN108084028B CN 108084028 B CN108084028 B CN 108084028B CN 201611046954 A CN201611046954 A CN 201611046954A CN 108084028 B CN108084028 B CN 108084028B
- Authority
- CN
- China
- Prior art keywords
- reaction
- compound
- solvent
- alkyl
- heteroaryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of a molecular glass photoresist containing a bisphenol A framework structure. The product is purified by solvent washing, filtering and purifying instead of a silica gel chromatographic column, so that the complexity of post-treatment is greatly reduced, the post-treatment time is shortened, and meanwhile, production personnel are protected from health hazards brought by silica gel. And the method greatly improves the yield of the compounds (III) and (V) under the condition of keeping the purity unchanged: the yield from the compound (I) to the compound (III) is improved by more than 15%, and the yield from the compound (IV) to the compound (V) is improved by more than 25%.
Description
Technical Field
The invention relates to a molecular glass photoresist containing a bisphenol A framework structure and a preparation method of the compound.
Background
The semiconductor industry has developed rapidly over the last half century due to the breakthrough of Integrated Circuit (IC) technology. Modern semiconductor technology requires smaller and smaller integrated circuits in electronic devices, higher and higher integration levels, and is expected to continue to advance according to moore's law. Moore's law has successfully guided the trends in the semiconductor industry and continues to continue its viability.
Since the 80's of the 20 th century, lithography has undergone a process of development from ultraviolet (UV, G-line 436nm and I-line 365nm) to deep ultraviolet (DUV, 248nm and 193nm), and the most influential extreme ultraviolet (EUV, 13.5nm) lithography among the next generation.
With the development of photolithography, the sensitivity, resolution and line edge roughness of 193nm lithography have been difficult to meet the requirements of the semiconductor industry. The euv lithography, which uses a light source of only 13.5nm, can reach the 32nm and 22nm technology nodes and even meet higher requirements, which makes euv lithography inevitably play an important role in the future lithography field.
The change of light source in the photolithography technology necessarily brings about the change of the structure of the photoresist, which the current photoresist has not been able to satisfy in the next generation technology. Due to the distinctive lithography technical characteristics of extreme ultraviolet lithography, the corresponding lithography materials also meet more stringent requirements. The extreme ultraviolet photoresist needs to have high resolution, high etching resistance, high sensitivity and low exposure dose (less than 10 mJ/cm)2) Low absorbance, high environmental stability, high transparency, low gassing, low line edge roughness (less than 1.5nm), and the like. Therefore, it is very urgent to develop an euv photoresist capable of satisfying the above requirements.
The molecular glass is a small molecular organic compound with higher glass transition temperature (Tg), has the dual advantages of small molecules and polymers, is in an amorphous state, has small molecular weight and monodispersity, has a glass transition process peculiar to high molecules, has high thermal stability, and is a very ideal photoresist material. Due to the excellent performance of the molecular glass photoresist, the molecular glass photoresist can be used in the traditional 248nm and 193nm photoetching technologies and is more likely to become the preferred main body material of the next generation photoetching technology (such as extreme ultraviolet photoetching, electron beam photoetching, nano-imprint photoetching and the like).
Patent ZL201210156675.6 reports a molecular glass containing bisphenol a framework structure and its synthesis method:
the method has the advantages of few reaction steps and few byproducts in the synthetic route, but the method has the defects of complex treatment after reaction, low reaction yield, harsh partial reaction conditions and the like, and is not suitable for industrial large-scale production.
Disclosure of Invention
The invention aims to provide a method for synthesizing a molecular glass photoresist containing a bisphenol A framework structure, which is economical and convenient and is suitable for industrial production.
The invention is an improved patent of Chinese patent ZL201210156675.6, and compared with the original patent, the synthetic route of the invention is simpler and easier, is convenient to operate and is suitable for industrial production.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a molecular glass photoresist containing a bisphenol A framework structure comprises the following steps:
wherein X is independently selected from H, C1-8Alkyl, -COOC1-8Alkyl, aryl, heteroaryl, and heteroaryl,R is independently selected from H, -OH, -OC1-8Alkyl, -OCOOC1-8Alkyl, aryl, heteroaryl, and heteroaryl,And at least one of the radicals R and-O-X is-OC1-8Alkyl, -OCOOC1-8Alkyl, aryl, heteroaryl, and heteroaryl,
R1Independently selected from H, -OC1-8An alkyl group; y is independently selected from C1-8An alkyl group; r2Independently selected from H or-OH;
(A) the tetrabromobisphenol A of the compound (I) is reacted with Z-Y in a solvent, wherein Y is C1-8Alkyl (such as methyl), Z is halogen (such as iodine), and after the reaction is finished, the obtained substance is directly used for the next reaction after the solvent is distilled off;
(B) reacting the material obtained in step (A) withIn a solvent, wherein R1Independently selected from H or-OC1-8An alkyl group; after the reaction is finished, extracting a product by using dichloromethane, and then carrying out spin drying to obtain a crude product; the crude product obtained is then washed with ethanol (for example 20-78 ℃) and filtered to obtain compound (III);
(C) dealkylation of the compound (III) obtained in step (B) to produce a compound (IV), wherein R2Independently selected from H or-OH;
(D) reacting the compound (IV) obtained in step (C) with (COOR)3)2O or R4Z is reacted, wherein R3Is optionally C1-8Alkyl radical, R4Is optionally C1-8Alkyl, aryl, heteroaryl, and heteroaryl,Z is halogen (preferably chlorine), and phenol type molecular glass with partially or completely protected hydroxyl groups is generated, namely the compound of the general formula (V); after the reaction is finished, adding an organic solvent and water (such as ethyl acetate and water or dichloromethane and water) into the reaction liquid, extracting and separating to obtain an organic phase, then performing rotary evaporation on the organic phase to obtain an oily substance, adding an organic solvent (preferably a solvent with a boiling point higher than 70 ℃, such as n-hexane) for insoluble products into the oily substance, and refluxing.
According to the invention, step (A) is preferably carried out in the presence of potassium carbonate, the solvent is preferably acetone, the reaction temperature is preferably 50-60 ℃, the reaction time is preferably 8-12h, and the feeding molar ratio of tetrabromobisphenol A to haloalkane (Z-Y) is preferably 1: 2.4.
According to the invention, step (B) is preferably carried out in the presence of a palladium catalyst, for example tetrakis (triphenylphosphine) palladium, preferably in the presence of a base, for example potassium carbonate, in a solvent, preferably dioxane-water, at a reaction temperature of preferably 90 to 100 ℃ for a time of preferably 8 to 24h, wherein the molar feed ratio of compound (II) to phenylboronic acid derivative is preferably 1: 6.
According to the invention, in the step (B), after the reaction is finished, the system is layered, and the organic phase is washed by using salt solution and is back-extracted by using dichloromethane; the aqueous phase was extracted with dichloromethane; all organic phases were combined and dried over anhydrous magnesium sulfate and rotary evaporated to give the crude product. Washing the obtained crude product with ethanol at 78 deg.C, and filtering to obtain white powder.
According to the invention, in step (C), the dealkylation is carried out in the presence of a Lewis acid, preferably the dealkylation is carried out using boron tribromide, preferably the boron tribromide is added dropwise at 0-10 ℃, the solvent used for the reaction is preferably dichloromethane, the reaction temperature is 0-35 ℃, and the reaction time is preferably 6-24 h.
According to the invention, in the step (C), the compound (III) and dichloromethane are mixed, boron tribromide is added into the mixed solution at 0 ℃ under the protection of nitrogen, and the mixed solution is returned to room temperature for reaction.
According to the present invention, step (D) is preferably carried out in the presence of 4-Dimethylaminopyridine (DMAP) or potassium carbonate, the reaction temperature is preferably 20-35 ℃ and the reaction solvent is preferably tetrahydrofuran.
According to the invention, after the reaction in step (D) is finished, ethyl acetate and water are added into the reaction liquid, and an organic phase is obtained by extraction and separation. The organic phase is washed with an aqueous sodium hydrogen sulfate solution (e.g., twice), and then with a saturated brine (e.g., twice). The organic phase is dried over anhydrous magnesium sulfate and rotary evaporated to an oil, n-hexane is added to the oil, the mixture is refluxed (for example, heated to 75 ℃ and refluxed for 8 hours), and the product is obtained after cooling and filtration.
According to the invention, the preparation method comprises the following steps:
(A) tetrabromobisphenol A and CH3Reacting Z in a solvent, wherein Z is halogen (such as iodine), and after the reaction is finished, directly using the substance obtained by distilling the solvent for the next reaction;
(B) reacting the substance obtained in the step (A) with 3, 4-dimethoxy phenylboronic acid in a solvent, extracting a product by using dichloromethane after the reaction is finished, and then spin-drying to obtain a crude product; the obtained crude product is washed with ethanol (e.g., 20-78 ℃), filtered to obtain compound (3);
(C) carrying out dealkylation on the compound (3) obtained in the step (B) to generate a compound (4);
(D) reacting the compound (4) obtained in the step (C) with di-tert-butyl dicarbonate to obtain a compound (5); after the reaction is finished, adding an organic solvent and water (such as ethyl acetate and water or dichloromethane and water) into the reaction liquid, extracting and separating to obtain an organic phase, then performing rotary evaporation on the organic phase to obtain an oily substance, adding an organic solvent (preferably a solvent with a boiling point of more than 70 ℃, such as n-hexane) for insoluble products into the oily substance, and refluxing.
Through a large number of experiments, the inventor finally realizes that the product is purified by washing, filtering and purifying the solvent to replace a silica gel chromatographic column, greatly reduces the complexity of post-treatment, reduces the post-treatment time, and simultaneously protects production personnel from health hazards brought by silica gel. Most importantly, the yield of the compounds (III) and (V) is greatly improved by the method under the condition of keeping the purity unchanged: the yield from the compound (I) to the compound (III) is improved by more than 15%, and the yield from the compound (IV) to the compound (V) is improved by more than 25%. And under the condition of ensuring the yield, the dropping temperature of the boron tribromide in the step (3) is increased from-78 ℃ to more than 0 ℃, so that the reaction condition is optimized, no side reaction occurs, and the cost of industrial production is greatly reduced.
The method has the advantages of reasonable process conditions, simple post-treatment operation, short reaction time, high reaction yield and no side reaction, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a graph of lithographic results below 35nm obtained by EUV lithography using the compound obtained in example 3 at a Shanghai synchrotron radiation light source 08U1B extreme ultraviolet light reticle station.
FIG. 2 is a graph of lithographic results below 25nm obtained by EUV lithography using the compound obtained in example 3 at the Shanghai synchrotron radiation light source 08U1B extreme ultraviolet reticle station. Is a graph of the results of below 25nm lithography.
FIG. 3 is a graph of lithographic results below 20nm obtained by EUV lithography using the compound obtained in example 3 at the Shanghai synchrotron radiation light source 08U1B extreme ultraviolet reticle station.
Detailed Description
The following series of specific examples are given to further illustrate the teaching of the present invention, but the present invention is not limited to these specific examples, and any modification of the present invention that would be obvious to those skilled in the art can be made to achieve similar results and is also included in the present invention.
Example 1
Preparation of Compound (2)
108.8g of tetrabromobisphenol A (0.2mol) and 55.2g of potassium carbonate (0.4mol) were put into a 1000ml three-necked flask, 200ml of acetone and 35ml of methyl iodide (0.44mol) were further added, and the mixture was reacted at 50 to 60 ℃ for 8 to 12 hours under reflux. After the reaction is finished, the acetone solvent is evaporated in a rotary mode and is directly used for the next reaction.
Preparation of Compound (3)
The solid obtained in the previous step was placed in a 1000ml three-necked flask, 174.7g of 3, 4-dimethoxyphenylboronic acid (0.96mol), 1.16g of tetrakis (triphenylphosphine) palladium (0.001mol) and 250ml of dioxane solvent were added, 220.8g of potassium carbonate (1.6mol) was dissolved in 250ml of water and then added to the reaction flask, and the reaction was carried out at 90-100 ℃ for 16 hours. After the reaction is finished, the system is layered, and the organic phase is washed three times by 200ml of saturated saline and back-extracted three times by 100ml of dichloromethane; the aqueous phase was extracted three times with dichloromethane. All organic phases were combined and dried over anhydrous magnesium sulfate and rotary evaporated to give the crude product. Washing the obtained crude product with ethanol at 78 deg.C for three times, filtering to obtain white powder, oven drying, weighing 143.2g, and purity over 99%. The total yield of the first two steps is 89.5 percent.
Comparative example 1:
preparation of Compound (2)
Adding 5.44g of tetrabromobisphenol A (10mmol) and 2.76g of potassium carbonate (20mmol) into a 150mL three-necked bottle, adding 50mL of acetone solvent and 4.26g of methyl iodide (30mmol), and carrying out reflux reaction at 50-60 ℃ for 10-15 h under the protection of argon. After the reaction, the acetone solvent was evaporated by rotary evaporation, and washed with 50mL of water, extracted with 50mL of dichloromethane three times, the organic layers were combined, dried over anhydrous magnesium sulfate, filtered and rotary evaporated to obtain a crude product, and subjected to silica gel column chromatography using ethyl acetate/petroleum ether to obtain 5.56g of a white solid powder, i.e., compound (2), with a yield of 96.2%.
Preparation of Compound (3)
5.72g of the compound (2) (10mmol) obtained above, 10.92g of 3, 4-dimethoxyphenylboronic acid (60mmol) and 0.58g of tetrakis (triphenylphosphine) palladium were put into a 250mL three-necked flask, and then 75mL of a 2M potassium carbonate solution and 75mL of a dioxane solvent were added, and the mixture was reacted at 90-100 ℃ for 48 hours under the protection of argon. Layering after the reaction is finished, and rotationally evaporating the dioxane solvent from the organic layer, washing with 100mL of distilled water, and extracting with 100mL of chloroform for three times; the aqueous layer was extracted three times with 50mL of chloroform. All organic layers were combined, dried over anhydrous magnesium sulfate, filtered and rotary-evaporated to give a crude product, which was subjected to silica gel column chromatography using ethyl acetate/petroleum ether as an eluent to give 5.94g of a white solid powder, i.e., compound (3), in 74.2% yield.
The overall yield in two steps was 71.4%.
Example 2
Preparation of Compound (4)
80g of the compound (3) (0.1mol) obtained in example 1 and 200ml of methylene chloride were charged into a 1000ml three-necked flask, and 300g of boron tribromide (1.2mol) was added under nitrogen protection at 0 ℃ to return to room temperature and reacted for 12 hours. After 12h, the reaction was transferred to a constant pressure dropping funnel, 300ml of water (0 ℃) was added to the three-necked flask, and then the reaction in the constant pressure funnel was slowly dropped into the three-necked flask, yielding a white solid in the water. Stirring for 4h after the dropwise addition. The white solid was dissolved by adding 500ml of ethyl acetate, and the mixture was allowed to stand to separate. The organic phase was washed five times with saturated brine to neutrality. The organic phase was dried over anhydrous magnesium sulfate and rotary evaporated to give 63g of product in 95.5% yield.
Comparative example 2
Preparation of Compound (4)
8.01g of the compound (3) (10mmol) obtained in comparative example 1 and 100mL of methylene chloride were charged in a 250mL three-necked flask, and 37.5g of boron tribromide (150mmol) were added under an argon atmosphere at-78 ℃ to return to room temperature and react for 12 hours. After the reaction, the reaction system was added to 100mL of 4N NaOH solution, the aqueous layer was separated, acidified with 5N hydrochloric acid, extracted three times with 100mL of ethyl acetate, the combined organic layers were dried over anhydrous magnesium sulfate, filtered and rotary evaporated to give 6.24g of white crystals with a yield of 94.4%.
Example 3
Preparation of Compound (5)
66g of the compound (4) (0.1mol) obtained in example 2 and 262g of di-tert-butyl dicarbonate (1.2mol) were charged in a 1000ml one-necked flask, 200ml of tetrahydrofuran was further added, and finally 1.22g of 4-Dimethylaminopyridine (DMAP) was added and reacted at room temperature for 12 hours. After the reaction, 300ml of ethyl acetate and 300ml of water were added to the reaction mixture, and a yellow organic phase was obtained by extraction separation. The organic phase was washed twice with a 1mol/L aqueous solution of sodium hydrogensulfate and twice with a saturated saline solution. Drying the obtained organic phase by using anhydrous magnesium sulfate, then carrying out rotary evaporation to obtain oily sticky matter, adding 500ml of n-hexane into the oily sticky matter, heating to 75 ℃, refluxing and boiling for 8 hours, cooling and filtering to obtain 130.4g of white product with the purity of more than 99%, wherein the yield of the reaction is 78.5%. 1H-NMR (400MHz, DMSO). delta.7.43 (s, 4H),7.41(a, 4H), 7.39(d, 4H), 7.35(d, 4H), 1.85(s, 6H), 1.48(s, 36H), 1.47(s, 36H), 1.11(s, 18H). Elemental analysis (C)89H112O30) C, 64.34 percent; h, 6.75%, found: c, 64.26%; h, 6.88 percent. The compound is used for EUV lithography in Shanghai synchrotron radiation light source 08U1B extreme ultraviolet light scribing station, and the result is shown in figures 1, 2 and 3.
Comparative example 3
Preparation of Compound (5)
6.61g of the compound (4) (10mmol) obtained in comparative example 2, 32.7g of di-tert-butyl dicarbonate (150mmol) and 0.45g of 4-Dimethylaminopyridine (DMAP) were charged into a 250mL three-necked flask, and 100mL of a tetrahydrofuran solvent was further added to react at room temperature under an argon atmosphere for 12 hours. After the reaction, the tetrahydrofuran solvent was evaporated by rotary evaporation, the remaining mixture was washed with 100mL of saturated brine, extracted three times with 100mL of dichloromethane, and the combined organic layers were dried over anhydrous magnesium sulfate, filtered, and rotary evaporated to give the crude product. Silica gel column chromatography using ethyl acetate/petroleum ether as eluent gave 7.83g of a white solid, 47.1% yield of the reaction.
According to the example 1 and the comparative example 1, in the process of preparing the compound (3) from the compound (I), the product containing the compound (2) obtained in the first step is directly screwed and put into the next step of reaction, so that the complicated post-treatment process is simplified, the loss of the product in the treatment process is reduced, and the yield of the compound (3) is improved.
As can be seen from comparative example 2, such dealkylation is usually carried out by reacting BBr at-78 deg.C3Was added dropwise to the reaction mixture, and in example 2, in the preparation of the compound (4) from the compound (3), the temperature of dropwise addition was raised from-78 ℃ to 0 ℃ and the yield was slightly increased. The cost of industrial production is greatly reduced by the increase of the dripping temperature, so that the production is more low-carbon and environment-friendly.
As can be seen from examples 1-3 and comparative examples 1-3, the present invention eliminates the use of silica gel chromatography to purify the product in the post-reaction treatment, and instead, the product is simply purified by washing and filtering with a suitable solvent. Greatly reduces the complexity of post-treatment, shortens the post-treatment time, and simultaneously protects production personnel from health hazards brought by silica gel. Most importantly, the method greatly improves the yield of the compounds (3) and (5) under the condition of keeping the purity unchanged, and comprises the following steps: the yield from compound (I) to compound (3) increased from 71.4% to 89.5%, and the yield from compound (4) to compound (5) increased from 47.1% to 78.5%.
Claims (15)
1. A process for the preparation of a compound of formula (V) comprising:
wherein X is independently selected from H, C1-8Alkyl, -COOC1-8Alkyl, aryl, heteroaryl, and heteroaryl,R is independently selected from H, -OH, -OC1-8Alkyl, -OCOOC1-8Alkyl, aryl, heteroaryl, and heteroaryl,And at least one of the radicals R and-O-X is-OC1-8Alkyl, -OCOOC1-8Alkyl, aryl, heteroaryl, and heteroaryl,
R1Independently selected from H, -OC1-8An alkyl group; y is independently selected from C1-8An alkyl group; r2Independently selected from H or-OH;
(A) reacting a compound (I) with Z-Y in a solvent, wherein Y is C1-8Alkyl, Z is halogen, and after the reaction is finished, the solvent is evaporated to obtain a substance which is directly used for the next reaction;
(B) reacting the material obtained in step (A) withIn a solvent, wherein R1Independently selected from H or-OC1-8An alkyl group; after the reaction is finished, extracting a product by using dichloromethane, and then carrying out spin drying to obtain a crude product; washing the obtained crude product with ethanol, and filtering to obtain a compound (III);
(C) dealkylation of the compound (III) obtained in the step (B) to produce a compound (IV), wherein R is2Independently selected from H or-OH;
(D) reacting the compound (IV) obtained in step (C) with (COOR)3)2O or R4Z is reacted, wherein R3Is optionally C1-8Alkyl radical, R4Is optionally C1-8Alkyl, aryl, heteroaryl, and heteroaryl,Z is halogen to produce a compound of formula (V); adding an organic solvent and water into the reaction liquid after the reaction is finished, wherein the organic solvent and the water are ethyl acetate and water or dichloromethane and water, extracting and separating to obtain an organic phase, performing rotary evaporation on the organic phase to obtain an oily substance, adding an organic solvent n-hexane insoluble in the product into the oily substance, and refluxing.
2. The method according to claim 1, wherein the reaction in step (A) is carried out in the presence of potassium carbonate.
3. The method according to claim 1, wherein the solvent is acetone and the reaction temperature is 50 to 60 ℃ in the step (A).
4. The production method according to claim 1, wherein the reaction in step (B) is carried out in the presence of a palladium catalyst.
5. The production method according to claim 1, wherein the step (B) is reacted in the presence of a base.
6. The process according to claim 1, wherein the reaction in step (B) is carried out in the presence of tetrakis (triphenylphosphine) palladium) and potassium carbonate, and the solvent is dioxane-water.
7. The preparation process according to claim 1, wherein in the step (B), after the reaction is completed, the system is layered, and the organic phase is washed with a salt solution and back-extracted with dichloromethane; the aqueous phase was extracted with dichloromethane; and (3) combining all organic phases, drying the organic phases by using anhydrous magnesium sulfate, carrying out rotary evaporation to obtain a crude product, washing the obtained crude product by using ethanol, and filtering the obtained product to obtain white powder.
8. The production process according to claim 1, wherein, in step (C), the dealkylation reaction is carried out in the presence of a Lewis acid.
9. The production process according to claim 8, wherein in the step (C), the dealkylation reaction is carried out using boron tribromide.
10. The production method according to claim 9, wherein in step (C), boron tribromide is added dropwise at 0 to 10 ℃.
11. The preparation process according to claim 9, wherein in the step (C), the compound (III) and dichloromethane are mixed, boron tribromide is added to the mixture at 0 ℃ under nitrogen protection, and the mixture is returned to room temperature for reaction.
12. The process according to claim 1, wherein the reaction in the step (D) is carried out in the presence of 4-Dimethylaminopyridine (DMAP) or potassium carbonate.
13. The process according to claim 1, wherein the reaction temperature in the step (D) is 20 to 35 ℃ and the reaction solvent is tetrahydrofuran.
14. The preparation method according to claim 1, wherein, after the reaction in step (D) is finished, ethyl acetate and water are added into the reaction solution, and an organic phase is obtained by extraction separation; washing the organic phase with sodium bisulfate aqueous solution and then with saturated brine; and drying the obtained organic phase by using anhydrous magnesium sulfate, then performing rotary evaporation to obtain an oily viscous substance, adding n-hexane into the oily viscous substance, refluxing, cooling and filtering to obtain the product.
15. The production method according to claim 1, wherein the production method comprises:
(A) tetrabromobisphenol A and CH3Reacting Z in a solvent, wherein Z is halogen, and after the reaction is finished, evaporating the solvent to obtain a substance which is directly used for the next reaction;
(B) reacting the substance obtained in the step (A) with 3, 4-dimethoxy phenylboronic acid in a solvent, extracting a product by using dichloromethane after the reaction is finished, and then spin-drying to obtain a crude product; washing the obtained crude product with ethanol, and filtering to obtain a compound (3);
(C) carrying out dealkylation on the compound (3) obtained in the step (B) to generate a compound (4);
(D) reacting the compound (4) obtained in the step (C) with di-tert-butyl dicarbonate to obtain a compound (5); after the reaction is finished, adding ethyl acetate and water or dichloromethane and water into the reaction liquid, extracting and separating to obtain an organic phase, then carrying out rotary evaporation on the organic phase to obtain an oily substance, adding an organic solvent n-hexane insoluble in the product into the oily substance, and refluxing.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611046954.1A CN108084028B (en) | 2016-11-23 | 2016-11-23 | Preparation method of molecular glass photoresist containing bisphenol A framework structure |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611046954.1A CN108084028B (en) | 2016-11-23 | 2016-11-23 | Preparation method of molecular glass photoresist containing bisphenol A framework structure |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108084028A CN108084028A (en) | 2018-05-29 |
CN108084028B true CN108084028B (en) | 2020-05-26 |
Family
ID=62170243
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611046954.1A Active CN108084028B (en) | 2016-11-23 | 2016-11-23 | Preparation method of molecular glass photoresist containing bisphenol A framework structure |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108084028B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114075155B (en) * | 2020-08-11 | 2023-08-01 | 中国科学院化学研究所 | Bisphenol A derivative, preparation method thereof and application thereof in lithography |
WO2024087158A1 (en) * | 2022-10-28 | 2024-05-02 | 中国科学院化学研究所 | High-etching-resistance silicon-containing molecular glass photoresist compound, and preparation method therefor and use thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07285918A (en) * | 1994-04-15 | 1995-10-31 | Shin Etsu Chem Co Ltd | Diphenolic acid t-butoxycarbonylmethyl ester derivative and its production |
CN103304385A (en) * | 2012-03-16 | 2013-09-18 | 中国科学院化学研究所 | Molecular glass photoresist containing bisphenol A skeleton structure as well as preparation method and application thereof |
-
2016
- 2016-11-23 CN CN201611046954.1A patent/CN108084028B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07285918A (en) * | 1994-04-15 | 1995-10-31 | Shin Etsu Chem Co Ltd | Diphenolic acid t-butoxycarbonylmethyl ester derivative and its production |
CN103304385A (en) * | 2012-03-16 | 2013-09-18 | 中国科学院化学研究所 | Molecular glass photoresist containing bisphenol A skeleton structure as well as preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN108084028A (en) | 2018-05-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103304385B (en) | Molecular glass photoresist containing bisphenol A skeleton structure as well as preparation method and application thereof | |
CN111094223B (en) | binaphthyl compounds | |
Cardineau et al. | Photolithographic properties of tin-oxo clusters using extreme ultraviolet light (13.5 nm) | |
KR101742473B1 (en) | Carbazole ketoxime ester high-photosensitivity photoinitiator | |
JP2019528331A (en) | Fluorene photoinitiator, method for producing the same, photocurable composition having the same, and use of fluorene photoinitiator in the field of photocuring | |
CN108084028B (en) | Preparation method of molecular glass photoresist containing bisphenol A framework structure | |
CN104557552A (en) | Starlike tetraphenylethylene derivative molecular glass, positive photoresist, positive photoresist coating and application thereof | |
CN102225924A (en) | Photoacid generators and photoresists comprising same | |
JPWO2014111980A1 (en) | Triptycene derivative useful as a self-assembled film forming material, its production method, film using it, and its production method | |
KR20150138220A (en) | Photobase generator | |
CN113200858B (en) | Synthesis based on triptycene derivative monomolecular resin, positive photoresist and application of positive photoresist in photoetching | |
JP5923823B2 (en) | Intermediate for acene dichalcogenophene derivative and synthesis method thereof | |
TWI745897B (en) | Photoinitiator composition comprising acylcarbazole derivative and carbazole oxime ester and application thereof in photocurable composition | |
EP3668906A1 (en) | Amide and imide photoinitiators | |
CN108341748B (en) | Monomolecular resin based on 1, 4-disubstituted column [5] arene derivative, positive photoresist and application thereof | |
CN117024380A (en) | Negative molecular glass photoresist compound based on hexabromotriptycene, and synthesis method and application thereof | |
CN108314785B (en) | Octaphenyl substituted cage-like silsesquioxane derivative molecular glass and application thereof | |
Schou et al. | On the phosphite-mediated synthesis of dithiafulvenes and π-extended tetrathiafulvalenes | |
CN109305955B (en) | Preparation method of molecular glass photoresist containing tetraphenylthiophenol structure | |
TW202019897A (en) | Photoinitiators | |
CN104144908B (en) | Spirofluorene derivative molecular glass and preparation method thereof and the application in photoetching | |
JP5377014B2 (en) | Method for producing chromene compound | |
CN112625022A (en) | Photoresist resin monomer and synthetic method thereof | |
JP2001328967A (en) | Method for producing highly pure alkyladamantyl ester | |
Speicher et al. | A synthesis-driven structure revision of ‘plagiochin E’, a highly bioactive bisbibenzyl |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |