Synthesis process of NA-04A
By introducing NA-04A into the photoresist material, the problem of insufficient performance of existing photoresist materials at the nano-level and EUV technology is solved, and higher photosensitiveness, resolution, mechanical strength and chemical resistance are achieved.
Patent Information
- Application Number
- CN202510018614.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-07
- Publication Date
- 2025-04-11
AI Technical Summary
At the nanoscale and more advanced EUV technology, existing photoresist materials are difficult to meet the high requirements of improving photosensitiveness, resolution, mechanical strength and chemical resistance.
By providing a synthesis process of NA-04A, NA-04A is an isomer of NA-04 and is used as a resin monomer in the field of photoresist. The pure product NA-04A is synthesized from NA-01 and NA-03A through a multi-step reaction process to improve the overall performance of the material.
The pure product NA-04A obtained through the NA-04A synthesis process is realized, further improving the photosensitiveness, resolution, mechanical strength and chemical resistance of the photoresist material, and meeting higher technical requirements.
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Figure CN119798198A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of organic synthesis and relates to a synthesis process of compound NA-04A. Background Art
[0002] Photoresist is one of the indispensable key materials in microelectronics manufacturing and is widely used in semiconductor chips, displays, optoelectronic devices and other precision manufacturing fields. NA-04, CAS No. 274247-93-7, Chinese name is hexahydro-6-[(2-methyl-1-oxo-2-propylene-1-yl)oxy]-2-oxo-methyl ester. The currently commercially available NA-04 is mainly used as a resin monomer in the field of photoresist. It reacts chemically under light of a specific wavelength through the synergistic effect with the photoinitiator to achieve the formation of photolithographic patterns. With the rapid development of integrated circuits, the nodes of semiconductor processes are constantly shrinking, from the early micron level to the current nanometer level and the more advanced EUV (extreme ultraviolet lithography) technology, which puts higher requirements on the performance of photoresist materials. As one of the core components of photoresist, the performance of resin monomers directly determines the key indicators of photoresist such as photosensitivity, resolution, mechanical strength and chemical resistance. Summary of the invention
[0003] The object of the present invention is to provide a synthesis process of compound NA-04A. The NA-04A provided by the present invention is an isomer of NA-04 and has the same application field as NA-04. As a resin monomer, it is mainly used in the field of photoresists. Pure NA-04A can be synthesized by the process of the present invention, thereby further improving the overall performance of the material.
[0004] A synthesis process of compound NA-04A, wherein the synthesis process of NA-04A is to first synthesize NA-01, then use NA-01 to synthesize NA-03A, and finally use NA-03A to synthesize NA-04A;
[0005] The chemical structural formula of NA-01 is as follows:
[0006]
[0007] The chemical structural formula of the NA-03A is as follows:
[0008]
[0009] The chemical structural formula of the NA04A is as follows:
[0010]
[0011] Furthermore, the synthesis method of NA-01 is:
[0012] At room temperature, methanol and NASM01 were added to the reaction bottle and mixed, and the mixture was stirred and heated for 18-30 hours. After the reaction was complete by LCMS, the reaction solution was concentrated at 45°C until no liquid flowed out, and dried at 40°C with air blowing to constant weight to obtain NA-01.
[0013] The chemical structural formula of NASM01 is as follows:
[0014]
[0015] Further, the ratio of methanol to NASM01 is 1.9:476 L / g;
[0016] Furthermore, the heating refers to heating to 35-45°C.
[0017] Furthermore, the synthesis method of NA-03A using NA-01 is:
[0018] (1) At room temperature, NA-01, tert-butyl alcohol, formic acid and hydrogen peroxide solution were added to a reaction bottle and mixed. The mixture was reacted for 14-18 hours. After the reaction was complete as determined by LCMS, deionized water and DCM were added and stirred for extraction and separation.
[0019] (2) After separation, DCM was added to the aqueous phase and stirred for extraction. The extraction was repeated twice. The organic phases obtained after the two extractions were combined, sodium thiosulfate was added and stirred overnight. The organic phase was filtered, and the filtrate was washed with deionized water until the KI test paper did not change color. Saturated brine was added for washing. Anhydrous sodium sulfate was added to the organic phase and dried for 0.5 h. After filtration, the filtrate was concentrated at 45° C. until no liquid flowed out, and dried at 45° C. to constant weight to obtain NA-03A.
[0020] Furthermore, the mass ratio of the NA-01, tert-butyl alcohol, formic acid, hydrogen peroxide solution, sodium thiosulfate and anhydrous sodium sulfate is 556:560:134.44:640:600:1000; the ratio of the NA-01, the deionized water in step (1), the DCM in step (1), the DCM added each time in step (2), the deionized water in step (2) and the saturated salt water is 556g:0.8-1L:1.8-2.2L:1.8-2.2L:500ml:500ml.
[0021] Furthermore, the synthesis method of NA-04A using NA-03A is:
[0022] At room temperature, DCM, NA-03A and DIPEA were added to the reaction bottle, nitrogen was introduced for replacement, the temperature was lowered, methacryloyl chloride was added dropwise, and the temperature was naturally restored to room temperature after the addition was completed to react for 14-18 hours. After the reaction was completed in LCMS, ice water was added dropwise at 10°C to quench, and 4 mol / L HCl was added to the organic phase after separation to adjust the pH to 3.8-4.2. After separation, saturated sodium bicarbonate aqueous solution was added to the organic phase for washing, and anhydrous sodium sulfate was added to the organic phase after separation for drying for 0.5 hours. After filtration, the filtrate was concentrated at 45°C until no liquid flowed out, and dried at 45°C to constant weight to obtain NA-04A.
[0023] Furthermore, the mass ratio of the NA-03A, DIPEA, methacryloyl chloride and anhydrous sodium sulfate is 420:307:227.57:500; the ratio of the NA-3A, DCM and saturated sodium carbonate aqueous solution is 420g:2.1L:2L.
[0024] Furthermore, the cooling refers to cooling to 0-10°C.
[0025] Furthermore, the dropping temperature of the methacryloyl chloride is 0-5°C.
[0026] Beneficial effects of the present invention:
[0027] The NA-04A provided by the present invention is an isomer of NA-04 and has the same application field as NA-04. As a resin monomer, it is mainly used in the field of photoresists. Pure NA-04A can be synthesized by the process of the present invention, further improving the overall performance of the material. BRIEF DESCRIPTION OF THE DRAWINGS
[0028] In order to facilitate understanding by those skilled in the art, the present invention is further described below with reference to the accompanying drawings.
[0029] Figure 1 Schematic diagram of the structural formula of the synthesis of NA-01 in Example 1;
[0030] Figure 2 Schematic diagram of the structural formula of the synthesis of NA-03A in Example 1;
[0031] Figure 3 Schematic diagram of the structural formula of the synthesis of NA-04A in Example 1;
[0032] Figure 4 It is a structural formula comparison diagram of NA-04A and NA-04 in Example 1;
[0033] Figure 5 is the HNMR spectrum of NA-04 in Example 1;
[0034] Figure 6This is the HNMR spectrum of NA-04A in Example 1. DETAILED DESCRIPTION
[0035] In order to further explain the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in conjunction with the accompanying drawings and preferred embodiments.
[0036] The reagents used in the embodiments of the present invention are all conventional reagents and can be directly purchased from the market.
[0037] Example 1
[0038] A synthesis process of compound NA-04A. The synthesis process of NA-04A in this embodiment is to first synthesize NA-01, then use NA-01 to synthesize NA-03A, and finally use NA-03A to synthesize NA-04A.
[0039] The synthesis method of NA-01 in this embodiment is:
[0040] At room temperature, 1.9L methanol and 476g NASM01 were added to a 3L reaction bottle, mixed, stirred and heated to 40°C, and reacted for 24h. After the reaction was completed by LCMS, the reaction solution was concentrated at 45°C until no liquid flowed out, and dried at 40°C to constant weight to obtain 556g of white solid NA-01 (yield: 97.73%). The structural diagram of the synthesis of NA-01 is shown in the attached figure. Figure 1 shown.
[0041] The synthesis method of NA-03A using NA-01 in this embodiment is:
[0042] (1) At room temperature, 556 g of NA-01, 560 g of tert-butyl alcohol, 134.44 g of formic acid and 640 g of 30% hydrogen peroxide solution were added to a 5 L reaction bottle and mixed. The mixture was reacted for 16 h. After the reaction was complete as controlled by LCMS, 1 L of deionized water and 2 L of DCM were added and stirred for extraction and separation.
[0043] (2) After separation, 2 L of DCM was added to the aqueous phase and stirred for extraction. The mixture was repeated twice. The organic phases obtained after extraction were combined, 600 g of sodium thiosulfate was added, and stirred overnight. The organic phase was filtered, and the filtrate was washed with 500 mL of deionized water until the KI test paper did not change color. 500 mL of saturated brine was added for washing. Then 1000 g of anhydrous sodium sulfate was added to the organic phase and dried for 0.5 h. After filtration, the filtrate was concentrated at 45° C. until no liquid flowed out, and dried at 45° C. to constant weight to obtain 425 g of white solid NA-03A (yield: 70.68%). The structural diagram of the synthesis of NA-03A is shown in the attached figure. Figure 2 shown.
[0044] The synthesis method of NA-04A using NA-03A in this embodiment is:
[0045] At room temperature, 2.1L of DCM, 420g of NA-03A and 307g of DIPEA were added to a 5L reaction bottle, nitrogen was introduced for replacement, the temperature was lowered to 5°C, 227.57g of methacryloyl chloride was added dropwise at 2.5°C, and the temperature was naturally restored to room temperature for reaction for 16h after the addition was completed. After the reaction was completed by LCMS, ice water was added dropwise at 10°C to quench, and 4mol / L HCl was added to the organic phase after separation to adjust the pH to 4, and 2L of saturated sodium bicarbonate aqueous solution was added to the organic phase after separation for washing, and 500g of anhydrous sodium sulfate was added to the organic phase after separation for drying for 0.5h. After filtration, the filtrate was concentrated at 45°C until no liquid flowed out, and dried at 45°C to constant weight by blowing to obtain 341g of off-white solid NA-04A (yield: 61.47%); the structural schematic diagram of the synthesis of NA-04A is shown in the attached figure Figure 3 shown.
[0046] Compare the structural formulas of NA-04 (CAS: 274247-93-7) and NA-04A prepared in this example (see Appendix Figure 4 ), it can be seen that the structure of NA-04A synthesized by this process is opposite to that of NA-04, and the results of nuclear magnetic resonance hydrogen spectrum analysis of NA-04 and NA-04A are as follows: Figure 5 and Figure 6 As shown by Figure 5 and Figure 6 It can be seen that in the spatial structure of NA-04 in HNMR, the hydrogen on the carbon at position 5 is far away from the oxygen at position 10 and is less affected by it. H =4.67ppm, and the hydrogen on the carbon at position 5 is closer to the oxygen at position 10 in the spatial structure of NA-04A, so it is more affected by it. H =5.14ppm.
[0047] Example 2
[0048] A synthesis process of compound NA-04A. The synthesis process of NA-04A in this embodiment is to first synthesize NA-01, then use NA-01 to synthesize NA-03A, and finally use NA-03A to synthesize NA-04A.
[0049] The synthesis method of NA-01 in this embodiment is:
[0050] At room temperature, 1.9 L methanol and 476 g NASM01 were added to a 3 L reaction bottle and mixed. The mixture was stirred and heated to 35 °C. The mixture was reacted for 18 h. After the reaction was completed as indicated by LCMS, the reaction solution was concentrated at 45 °C until no liquid flowed out. The mixture was dried at 40 °C to constant weight to obtain 552 g of white solid NA-01 (yield: 97.03%).
[0051] The synthesis method of NA-03A using NA-01 in this embodiment is:
[0052] (1) At room temperature, 556 g of NA-01, 560 g of tert-butyl alcohol, 134.44 g of formic acid and 640 g of 30% hydrogen peroxide solution were added to a 5 L reaction bottle and mixed. The mixture was reacted for 14 h. After the reaction was complete as controlled by LCMS, 0.8 L of water and 1.8 L of DCM were added and stirred for extraction and separation.
[0053] (2) After separation, 1.8 L of DCM was added to the aqueous phase and stirred for extraction. This was repeated twice. The organic phases obtained after the two extractions were combined, 600 g of sodium thiosulfate was added, and stirred overnight. The organic phase was filtered, and the filtrate was washed with 500 mL of deionized water until the KI test paper did not change color. 500 mL of saturated brine was added for washing. Then 1000 g of anhydrous sodium sulfate was added to the organic phase and dried for 0.5 h. After filtration, the filtrate was concentrated at 45° C. until no liquid flowed out, and dried at 45° C. to constant weight to obtain 420 g of white solid NA-03A (yield: 69.85%).
[0054] The synthesis method of NA-04A using NA-03A in this embodiment is:
[0055] At room temperature, 2.1L of DCM, 420g of NA-03A and 307g of DIPEA were added to a 5L reaction bottle, nitrogen was introduced for replacement, the temperature was lowered to 0°C, 227.57g of methacryloyl chloride was added dropwise at 0°C, and the temperature was naturally restored to room temperature for reaction for 14h after the addition was completed. After the reaction was completed in LCMS, ice water was added dropwise at 10°C to quench, and 4mol / L of HCl was added to the organic phase after separation to adjust the pH to 3.8. After separation, 2L of saturated sodium bicarbonate aqueous solution was added to the organic phase for washing, and 500g of anhydrous sodium sulfate was added to the organic phase after separation and dried for 0.5h. After filtration, the filtrate was concentrated at 45°C until no liquid flowed out, and dried to constant weight at 45°C to obtain 338g of off-white solid NA-04A (yield: 60.93%).
[0056] Example 3
[0057] A synthesis process of compound NA-04A. The synthesis process of NA-04A in this embodiment is to first synthesize NA-01, then use NA-01 to synthesize NA-03A, and finally use NA-03A to synthesize NA-04A.
[0058] The synthesis method of NA-01 in this embodiment is:
[0059] At room temperature, 1.9 L methanol and 476 g NASM01 were added to a 3 L reaction bottle and mixed. The mixture was stirred and heated to 45 °C. The reaction was allowed to react for 30 h. After the reaction was completed as controlled by LCMS, the reaction solution was concentrated at 45 °C until no liquid flowed out. The mixture was dried at 40 °C to constant weight to obtain 556.8 g of white solid NA-01 (yield: 97.87%).
[0060] The synthesis method of NA-03A using NA-01 in this embodiment is:
[0061] (1) At room temperature, 556 g of NA-01, 560 g of tert-butyl alcohol, 134.44 g of formic acid and 640 g of 30% hydrogen peroxide solution were added to a 5 L reaction bottle and mixed. The mixture was reacted for 18 h. After the reaction was complete as controlled by LCMS, 1.2 L of deionized water and 2.2 L of DCM were added and stirred for extraction and separation.
[0062] (2) After separation, 2.2 L of DCM was added to the aqueous phase and stirred for extraction. This was repeated twice. The organic phases obtained after the two extractions were combined, 600 g of sodium thiosulfate was added, and stirred overnight. The organic phase was filtered, and the filtrate was washed with 500 mL of deionized water until the KI test paper did not change color. 500 mL of saturated brine was added for washing. Then 1000 g of anhydrous sodium sulfate was added to the organic phase and dried for 0.5 h. After filtration, the filtrate was concentrated at 45° C. until no liquid flowed out, and dried at 45° C. to constant weight to obtain 423 g of white solid NA-03A (yield: 70.35%).
[0063] The synthesis method of NA-04A using NA-03A in this embodiment is:
[0064] At room temperature, 2.1L of DCM, 420g of NA-03A and 307g of DIPEA were added to a 5L reaction bottle, nitrogen was introduced for replacement, the temperature was lowered to 10°C, 227.57g of methacryloyl chloride was added dropwise at 5°C, and the temperature was naturally restored to room temperature for reaction for 18h after the addition was completed. After the reaction was completed in LCMS, ice water was added dropwise at 10°C to quench, and 4mol / L HCl was added to the organic phase after separation to adjust the pH to 4.2. After separation, 2L of saturated sodium bicarbonate aqueous solution was added to the organic phase for washing, and 500g of anhydrous sodium sulfate was added to the organic phase after separation and dried for 0.5h. After filtration, the filtrate was concentrated at 45°C until no liquid flowed out, and dried to constant weight at 45°C to obtain 340.2g of off-white solid NA-04A (yield: 61.33%).
[0065] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.
Claims
1. A synthesis process of compound NA-04A, characterized in that: The synthesis process of NA-04A is to first synthesize NA-01, then use NA-01 to synthesize NA-03A, and finally use NA-03A to synthesize NA-04A; The chemical structural formula of NA-01 is as follows: The chemical structural formula of the NA-03A is as follows: The chemical structural formula of the NA04A is as follows:
2. The synthesis process of the compound NA-04A according to claim 1, characterized in that: The synthesis method of NA-01 is: At room temperature, methanol and NASM01 were added to the reaction bottle and mixed, and the mixture was stirred and heated for 18-30 hours. After the reaction was complete by LCMS, the reaction solution was concentrated at 45°C until no liquid flowed out, and dried at 40°C with air blowing to constant weight to obtain NA-01. The chemical structural formula of NASM01 is as follows:
3. The synthesis process of the compound NA-04A according to claim 2, characterized in that: The ratio of methanol to NASM01 is 1.9:476 L / g.
4. The synthesis process of the compound NA-04A according to claim 2, characterized in that: The heating refers to heating to 35-45°C.
5. The synthesis process of the compound NA-04A according to claim 1, characterized in that: The synthesis method of NA-03A using NA-01 is as follows: (1) At room temperature, NA-01, tert-butyl alcohol, formic acid and hydrogen peroxide solution were added to a reaction bottle and mixed. The mixture was reacted for 14-18 hours. After the reaction was complete as determined by LCMS, deionized water and DCM were added and stirred for extraction and separation. (2) After separation, DCM was added to the aqueous phase and stirred for extraction. The extraction was repeated twice. The organic phases obtained after the two extractions were combined, sodium thiosulfate was added and stirred overnight. The organic phase was filtered, and the filtrate was washed with deionized water until the KI test paper did not change color. Saturated brine was added for washing. Anhydrous sodium sulfate was added to the organic phase and dried for 0.5 h. After filtration, the filtrate was concentrated at 45° C. until no liquid flowed out, and dried at 45° C. to constant weight to obtain NA-03A.
6. The synthesis process of the compound NA-04A according to claim 5, characterized in that: The mass ratio of the NA-01, tert-butyl alcohol, formic acid, hydrogen peroxide solution, sodium thiosulfate and anhydrous sodium sulfate is 556:560:134.44:640:600:1000; the ratio of the NA-01, the deionized water in step (1), the DCM in step (1), the DCM added each time in step (2), the deionized water in step (2) and the saturated salt water is 556g:0.8-1L:1.8-2.2L:1.8-2.2L:500ml:500ml.
7. The synthesis process of the compound NA-04A according to claim 1, characterized in that: The synthesis method of synthesizing NA-04A using NA-03A is: At room temperature, DCM, NA-03A and DIPEA were added to the reaction bottle, nitrogen was introduced for replacement, the temperature was lowered, methacryloyl chloride was added dropwise, and the temperature was naturally restored to room temperature after the addition was completed to react for 14-18 hours. After the reaction was completed in LCMS, ice water was added dropwise at 10°C to quench, and 4 mol / L HCl was added to the organic phase after separation to adjust the pH to 3.8-4.
2. After separation, saturated sodium bicarbonate aqueous solution was added to the organic phase for washing, and anhydrous sodium sulfate was added to the organic phase after separation for drying for 0.5 hours. After filtration, the filtrate was concentrated at 45°C until no liquid flowed out, and dried at 45°C to constant weight to obtain NA-04A.
8. The synthesis process of the compound NA-04A according to claim 7, characterized in that: The mass ratio of the NA-03A, DIPEA, methacryloyl chloride and anhydrous sodium sulfate is 420:307:227.57:500; the ratio of the NA-3A, DCM and saturated sodium carbonate aqueous solution is 420g:2.1L:2L.
9. The synthesis process of the compound NA-04A according to claim 7, characterized in that: The cooling refers to cooling to 0-10°C.
10. The synthesis process of the compound NA-04A according to claim 7, characterized in that: The dropping temperature of the methacryloyl chloride is 0-5°C.