CN101943862B - Sulfonium salt photo-acid generator using stilbene as main body and preparation method thereof - Google Patents
Sulfonium salt photo-acid generator using stilbene as main body and preparation method thereof Download PDFInfo
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- CN101943862B CN101943862B CN2010102844410A CN201010284441A CN101943862B CN 101943862 B CN101943862 B CN 101943862B CN 2010102844410 A CN2010102844410 A CN 2010102844410A CN 201010284441 A CN201010284441 A CN 201010284441A CN 101943862 B CN101943862 B CN 101943862B
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Abstract
The invention relates to a sulfonium salt photo-acid generator using stilbene as the main body and a preparation method thereof, which discloses a design and preparation method of a sulfonium salt photo-acid generator using stilbene chromophore as the main body and having two-photon absorption capability, in particular to a novel photo-acid generator synthesized by using stilbene as the conjugated chain bridge, adding various electron donors on para positions of the benzene ring and using sulfonium salts with different substituent groups as electron acceptors and a preparation method thereof. The photo-acid generator can be well dissolved in a common solvent such as dichloromethane, trichloromethane, acetone and tetrahydrofuran, and has the advantages of simple synthesis procedure, easy purification, high yield and the like. Because the photo-acid generator has a push-pull type molecular structure and the molecule indicates the two-photon absorption properties of the stilbene compound, the photo-acid generator has great application values in the fields of single-photon photoetching and two-photon photoetching.
Description
Technical field
The present invention relates to one type is sulfosalt class photo-acid agent of main body and preparation method thereof with the talan.
Background technology
Photo-acid agent is progressively developed the eighties in 20th century; Because of itself having good chemical amplification characteristics, and be widely used in chemical amplification imaging system such as miniature carving technology, the scale integrated circuit manufacturing; Microelectronics; Microfluidics, fields such as optical storage of data are one of indispensable important raw and processed materials of hyundai electronics areas of information technology.Wherein, sulfosalt is one type of photo-acid agent that is widely used.Because the two photon absorption cross section value of commercially available photo-acid agent is very little usually, can not be applied to two-photon photoetching field, this has limited it greatly in some applications, like the application on three-dimensional fine processing, the micro mechanical system.In order to improve its two-photon absorption performance, people have taked a lot of methods that photogenerated acid has been carried out modification.
In recent years, be that the photo-acid agent of parent has received people's attention with the talan structure.It is the conjugation chain bridge that the Marder of the U.S. and Perry research group have synthesized with the talan, and triphenylamine is the BSB-S of electron donor
2Sulfosalt type photo-acid agent (Wenhui Zhou, et al. Science, 2002,296,1106).Because the molecular structure of its D-π-D (D is an electron donor) has increased the intramolecular charge transfer greatly; Thereby give the characteristic of photo-acid agent two-photon excitation; Make photo-acid agent in the more low-yield generation that can cause light acid down, and have good product acid efficient.In addition; Relevant Theoretical Calculation learns, if be that D-π-A (A is an electron accepter) result can shift by more effective realization intramolecular charge with D-π-D structural change, better strengthens the two-photon excitation performance; Thereby the photo-acid agent that obtained performance is more excellent (Pond SJK; Et al. J. Am. Chem. Soc., 2004,126:9291).So exploitation is the conjugation chain bridge with the talan, the photo-acid agent with electronics push-pull configuration becomes inevitable developing direction.
Summary of the invention
The object of the present invention is to provide one type to be sulfosalt class photo-acid agent of main body and preparation method thereof with the talan.
It is the conjugation chain bridge that the present invention selects with the talan, through in the phenyl ring contraposition, adding electron donor, has synthesized novel photo-acid agent in conjunction with the sulfosalt with different substituents as electron accepter, aims to provide the photo-acid agent with the acid ability of outstanding pair of light assets.
One type of the present invention's proposition is the sulfosalt class photo-acid agent of main body with the talan, and said sulfosalt class photo-acid agent has following chemical formula:
Wherein: R
1Can in methoxyl, ethoxy, butoxy, benzyloxy, own oxygen base, octyloxy, hydroxyl or the acetoxyl group any; R
2Can in methyl, benzyl or the 4-cyanic acid benzyl any; R
3For in the negative ion such as trifluoromethayl sulfonic acid root, hexafluoro-phosphate radical or tetrafluoroborate any.
One type of the present invention's proposition is the preparation method of the sulfosalt class photo-acid agent of main body with the talan, and concrete steps are following:
(1) 4-hydroxy benzaldehyde and 1-1.2 times of equivalent alkane iodide are dissolved in the acetone, and add sal tartari, stir refluxed reaction 4 ~ 8 hours; The inorganic salts composition of solids removed by filtration, acetone is removed in decompression distillation, obtains weak yellow liquid 4-alkoxy benzene formaldehyde;
(2) under the inert gas shielding, methyltriphenylphospbromide bromide phosphorus is dissolved in the dimethyl sulfoxide, adds 1-1.2 times of equivalent sodium hydride under the stirring at room; System is heated to 85 ~ 90 ℃ of reactions 0.5 ~ 1 hour afterwards, and reaction system no longer includes gas and emits, and it is slowly cooled to room temperature; Drip step (1) products therefrom 4-alkoxy benzene formaldehyde; Continue reaction 2 ~ 4 hours after dripping, reaction system is poured in the water into ethyl acetate extraction; Organic phase is used anhydrous sodium sulfate drying, and column chromatography obtains faint yellow oily product 4-alkoxystyrene;
(3) under the inert gas shielding; In step (2) products therefrom 4-alkoxystyrene, add triethanolamine as solvent, add 1-1.2 times of equivalent 4-bromobenzene dimethyl sulfide and palladium again, be heated with stirring to 100 ~ 120 ℃; React after 12 ~ 24 hours; Pour in the water, filter, solid obtains white powder product 4-(4 '-alkoxystyrene base) thioanisole through recrystallization; The palladium addition is the 1%-1.2% of 4-alkoxystyrene quality;
(4) step (3) product is dissolved in the anhydrous methylene chloride, adds 1-1.2 times of equivalent halogenated alkane or halogenated aryl hydrocarbon and 1-1.2 times of equivalent trifluoro-methane sulfonic acid silver successively, the lucifuge stirring at room was removed methylene chloride after 12 ~ 24 hours; Add acetonitrile and stir, solids removed by filtration is added dropwise in the absolute ether behind the concentrated solvent acetonitrile; Produce white precipitate, dry behind the collecting precipitation, be dissolved in once more in the acetone; In drips of solution being added in the saturated aqueous solution of salt; Produce white precipitate, filter the back and obtain white powder, promptly get required product.
Among the present invention, the said alkane iodide of step (1) be in iodomethane, iodoethane or the iodobutane etc. any.
Among the present invention, said halogenated alkane can adopt iodomethane, and said halogenated aryl hydrocarbon can adopt in benzyl bromine or the 4-cyanic acid benzyl bromine any.
Among the present invention, the saturated aqueous solution of said salt adopts hexafluorophosphoric acid potassium solution or tetrafluoro boric acid sodium solution.
Among the present invention, inert gas is a nitrogen described in step (2) and the step (3).
Among the present invention, the ratio of absolute ether and acetonitrile solution is the ether volume in the step (4): the acetonitrile solution volume is 10:1.
Among the present invention, the saturated aqueous solution of salt and the ratio of acetone soln are the saturated aqueous solution volume in the step (4): the acetone soln volume is 25:1.
Among the present invention, described methyltriphenylphospbromide bromide phosphorus, palladium, 4-bromobenzene dimethyl sulfide, halogenated alkane, halogenated aryl hydrocarbon, trifluoro-methane sulfonic acid silver, Potassium Hexafluorophosphate and sodium tetrafluoroborate are the commercially available prod.
Characteristics of the present invention are:
1. selecting group such as ethoxy is electron donor, and sulfosalt is an electron accepter, and talan is the conjugation chain bridge, has synthesized the novel also photo-acid agent of report not.As typical D-π-A structure, has the acid ability of good product;
2. preparation process is fairly simple, and reaction yield is higher;
3. have the fine solubility ability, can be dissolved in tetrahydrofuran, methylene chloride is in many common solvents such as acetone;
4. have very high chemical stability, under the condition of dark room temperature, can keep long preservation.
Description of drawings
Fig. 1 is the nmr spectrum of target product in the embodiment of the invention 1.
Fig. 2 is the photolysis and the photogenerated acid ultraviolet-visible absorption spectroscopy of target product in the embodiment of the invention 1.
Embodiment
Below with instantiation as the present invention is further explained, but should not regard as qualification of the present invention.
Embodiment 1
Parent material is the 4-hydroxy benzaldehyde, obtains intermedium 4-alkoxystyrene through Williamson reaction and Wittig reaction, through the Heck reaction it is connected with 4-bromobenzene dimethyl sulfide, and then obtains the photo-acid agent of diphenylethylene; R in the present embodiment
1Be ethoxy, R
2Be 4-cyanic acid benzyl, R
3Be hexafluoro-phosphate radical, its synthetic route is represented as follows:
In the formula:
I: iodoethane, sal tartari, acetone refluxed 4 hours;
Ii: methyltriphenylphospbromide bromide phosphorus, sodium hydride, dimethyl sulfoxide, room temperature was reacted 2 hours;
Iii:4-bromobenzene dimethyl sulfide, palladium, triethanolamine, reacted 24 hours by 120 ℃;
Iv: trifluoro-methane sulfonic acid silver, 4-cyanic acid benzyl bromine, Potassium Hexafluorophosphate, methylene chloride, room temperature was reacted 24 hours.
1. prepare the 4-ethoxy-benzaldehyde
In 100mL single port bottle, 6.0g 4-hydroxy benzaldehyde (0.05mol) and 8.5g iodoethane (0.055mol) are dissolved in the 50ml acetone, add 10.5g sal tartari (0.075mol) again, be heated to 70 ℃ of back flow reaction 4 hours.Thin plate chromatography detection reaction finishes.Filter out inorganic salts, solvent evaporated vacuumizes 30min.Get weak yellow liquid 4-ethoxy-benzaldehyde, productive rate: 90%.
2. prepare 4-ethoxybenzene ethene
In the 250mL three-necked bottle, add 21.0g trityl group phosphonium bromide (60mmol), 2.8g successively, 60% sodium hydride (70 mmol) and 80mL dimethyl sulfoxide, stirring at room reaction under the nitrogen protection, finding has a large amount of gases to emit.After 10 minutes, place 85 ℃ of oil baths to stir, discovery gas is overflowed the system flavescence in a large number.Wait not have and be cooled to room temperature after gas continues to overflow.Freshly prepd 4-ethoxy-benzaldehyde is dissolved in the 10mL dimethyl sulfoxide again it joined in this system, about 2 hours of stirring at room, thin plate chromatography detection reaction finishes.With ethyl acetate extraction twice, evaporate to dryness behind the anhydrous sodium sulfate drying, column chromatography for separation gets faint yellow oily product 4-ethoxybenzene ethene 5.5g, productive rate: 68%.
1H?NMR（CDCl
3,?δ
ppm）:?7.3194?(d,?2H,?PhH); 6.8329?(d,?2H,?PhH); 6.6731?(m,?1H,?CH=);?5.6043?(d,?1H,?CH=);?5.1080 (d,?1H,?CH=);?4.0146?(q,?2H,?CH
2);?1.3812?(t,?3H,?CH
3)
3. prepare 4-(4-ethoxybenzene vinyl) thioanisole
In 100mL single port bottle, add 1.48g 4-ethoxybenzene ethene (10mmol), 2.2g 4-bromobenzene dimethyl sulfide (11mmol), 20mg palladium, 30mL triethanolamine successively; At room temperature vacuumize then-Tong nitrogen circulation three times after; Place 120 ℃ of oil bath lucifuges of preheating to react 24 hours in flask, thin plate chromatography detection reaction finishes.In a large amount of deionized waters of product impouring, leave standstill, cross and filter head product.Head product is dissolved in the methylene chloride, utilizes the silica gel short column to remove palladium, get weak yellow liquid.Solvent evaporated with methenyl choloride and ethyl alcohol recrystallization, gets white solid product 4-(4-ethoxybenzene vinyl) thioanisole 1.7g, productive rate: 63%.
1H?NMR（CDCl
3,?δ
ppm）:?7.4336?(d,?2H,?PhH);?7.4122?(d,?2H,?PhH);?7.2396?(d,?2H,?PhH);?7.0374?(d,?1H,?CH=);?6.9340?(d,?1H,?CH=);?6.8911?(d,?2H,?PhH);?4.0788?(q,?2H,?CH
2);?2.4961?(S,?3H,?CH
3);?1.4222?(t,?3H,?CH
3)
4. prepare the target photo-acid agent
In a 100mL single port bottle, add 270mg 4-(4-ethoxybenzene vinyl) thioanisole (1mmol), 215.6mg 4-cyanic acid benzyl bromine (1.1mmol) and 40mL methylene chloride.Behind the freezing 30min, the trifluoro-methane sulfonic acid silver of 282.7mg is joined in the system, the room temperature lucifuge stirred 24 hours, and thin plate chromatography detection reaction finishes.With the methylene chloride evaporate to dryness, with the acetonitrile dissolving, remove by filter silver salt, concentrated filtrate with the ether sedimentation of 10 times of volumes, gets the 415mg crude product, once more with acetonitrile dissolving, ether sedimentation.Get the 300mg sulfosalt, productive rate 51%.Directly carry out salt exchange (twice), get the 250mg sulfosalt and be dissolved in the small amount of acetone, it is slowly splashed in the saturated hexafluorophosphoric acid aqueous solutions of potassium of 25 times of volumes of stirring.Have deposition to separate out, filter, drying gets white powder 200mg, is target product.Productive rate: 80.6%.
1H?NMR（CD
3CN,?δ
ppm）:?7.7962?(d,?2H,?PhH);?7.7517?(d,?2H,?PhH);?7.6945?(d,?2H,?PhH);?7.5750?(d,?2H,?PhH);?7.4325?(d,?1H,?CH=);?7.4010?(d,?2H,?PhH);?7.1634?(d,?1H,?CH=);?6.9934?(d,?2H,?PhH);?4.9461?(d,?1H,?CH
2)?;?4.7679?(d,?1H,?CH
2)?;?4.1351?(q,?2H,?CH
2);?3.2214?(S,?3H,?CH
3);?1.4029?(t,?3H,?CH
3)
Embodiment 2
Identical with embodiment 1 preparation method, just when preparation target photogenerated acid, 4-cyanic acid benzyl bromine is replaced to the iodomethane of equivalent, all the other steps are constant, then synthesize methyl substituted target photo-acid agent after handling.
Embodiment 3
Identical with embodiment 1 preparation method, just when preparation alkoxy benzene formaldehyde, iodoethane is replaced to iodomethane, all the other step inconvenience then synthesize the substituted target photo-acid agent of 4-methoxyl after handling meticulously.
With rhodamine B is sour indicator, uses the 365nm ultraviolet light to be excitation source, and the photogenerated acid quantum yield that records the material among the embodiment 1-embodiment is respectively 0.40.
Claims (6)
1. one type of sulfosalt class photo-acid agent that is the main body with talan chromophore is characterized in that the structural formula of said sulfosalt class photo-acid agent is:
Wherein: R
1For in methoxyl, ethoxy, butoxy, benzyloxy, own oxygen base, octyloxy, hydroxyl or the acetoxyl group any; R
2For in methyl, benzyl or the 4-cyanic acid benzyl any; R
3For in trifluoromethayl sulfonic acid root, hexafluoro-phosphate radical or the tetrafluoroborate any.
2. the preparation method of one type of sulfosalt class photo-acid agent that is the main body with talan chromophore according to claim 1, its characteristic concrete steps are following:
(1) 4-hydroxy benzaldehyde and 1-1.2 times of equivalent alkane iodide are dissolved in the acetone, and add sal tartari, stir refluxed reaction 4-8 hour; The inorganic salts composition of solids removed by filtration, acetone is removed in decompression distillation, obtains weak yellow liquid 4-alkoxy benzene formaldehyde;
(2) under the inert gas shielding, methyltriphenylphospbromide bromide phosphorus is dissolved in the dimethyl sulfoxide, adds 1-1.2 times of equivalent sodium hydride under the stirring at room; System is heated to 85 ~ 90 ℃ of reactions 0.5 ~ 1 hour afterwards, and reaction system no longer includes gas and emits, and it is slowly cooled to room temperature; Drip step (1) products therefrom 4-alkoxy benzene formaldehyde; Continue reaction 2-4 hour after dripping, reaction system is poured in the water into ethyl acetate extraction; Organic phase is used anhydrous sodium sulfate drying, and column chromatography obtains faint yellow oily product 4-alkoxystyrene;
(3) under the inert gas shielding; In step (2) products therefrom 4-alkoxystyrene, add triethanolamine as solvent, add 1-1.2 times of equivalent 4-bromobenzene dimethyl sulfide and palladium again, be heated with stirring to 100-120 ℃; React after 12-24 hour; Pour in the water, filter, solid obtains white powder product 4-(4 '-alkoxystyrene base) thioanisole through recrystallization; The palladium addition is the 1%-1.2% of 4-alkoxystyrene quality;
(4) step (3) product is dissolved in the anhydrous methylene chloride, adds 1-1.2 times of equivalent halogenated alkane or halogenated aryl hydrocarbon and 1-1.2 times of equivalent trifluoro-methane sulfonic acid silver successively, the lucifuge stirring at room was removed methylene chloride after 12 ~ 24 hours; Add acetonitrile and stir, solids removed by filtration is added dropwise in the absolute ether behind the concentrated solvent acetonitrile; Produce white precipitate, dry behind the collecting precipitation, be dissolved in once more in the acetone; Drips of solution is added in the saturated aqueous solution of salt; Produce white precipitate, filter the back and obtain white powder, promptly get required product.
3. preparation method according to claim 2, it is characterized in that the said alkane iodide of step (1) be in iodomethane, iodoethane or the iodobutane any.
4. preparation method according to claim 2 is characterized in that said halogenated alkane adopts iodomethane, and said halogenated aryl hydrocarbon adopts in benzyl bromine or the 4-cyanic acid benzyl bromine any.
5. preparation method according to claim 2 is characterized in that the saturated aqueous solution of said salt adopts hexafluorophosphoric acid potassium solution or tetrafluoro boric acid sodium solution.
6. preparation method according to claim 2 is characterized in that inert gas is a nitrogen described in step (2) and the step (3).
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| CN102141731A (en) * | 2011-02-23 | 2011-08-03 | 同济大学 | Toluylene-containing meta-substituted sulfonium salt photoproduction acid agent and preparation method thereof |
| CN103217868A (en) * | 2013-03-19 | 2013-07-24 | 同济大学 | Photoacid generator containing double-branched sulfonium salt, preparation method and application thereof |
| CN106458879A (en) * | 2014-05-13 | 2017-02-22 | 东洋合成工业株式会社 | Onium salt, photoacid generator, photosensitive resin composition, and method for producing device |
| CN104181772B (en) * | 2014-08-15 | 2018-07-03 | 同济大学 | Two-photon activity photo-acid agent of the one kind using biphenyl as conjugated structure, preparation method and applications |
| CN104238268B (en) * | 2014-08-15 | 2017-12-26 | 同济大学 | Sulfosalt class photo-acid agent based on triphenylethylene, preparation method and applications |
| CN104478772A (en) * | 2014-11-19 | 2015-04-01 | 同济大学 | Preparation method and application of photo-produced acidic agent having single and double photon activity and containing dual-branched sulfonium salt |
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| CN110105256B (en) * | 2019-04-30 | 2020-11-03 | 同济大学 | Alpha-aminoketone-stilbene sulfonium salt compound and preparation method and application thereof |
| CN110078761B (en) * | 2019-04-30 | 2021-06-04 | 同济大学 | Acyl phosphine oxide-stilbene sulfonium salt compound and preparation method and application thereof |
| CN112961085B (en) * | 2021-02-18 | 2022-02-01 | 同济大学 | LED excitable intramolecular sensitization type sulfonium salt compound and preparation method and application thereof |
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| US7833690B2 (en) * | 2001-11-05 | 2010-11-16 | The University Of North Carolina At Charlotte | Photoacid generators and lithographic resists comprising the same |
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