Sulfonium salt containing pyrazoline groups and preparation method and application thereof

A technology of sulfonium salt and pyrazoline, applied in the field of new material organic chemicals, can solve the problems of difficulty in synthesis, difficulty in industrialized production, low yield and the like

Active Publication Date: 2019-05-21
TONGJI UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the conjugated system of sulfonium salts that have been commercially used at present is relatively small, so that the absorption wavelength of its main absorption peak is relatively small, which cannot meet its application in the long-wavelength field.
The currently designed and synthesized sulfonium salts with larger wavelength absorption peaks are mainly sulfonium salts with D-π-A (D is electron donor, A is electron acceptor) structure (Wu X.Y., Jin M .,Xie J.C.,Malvel J.P.,Wan D.C.,Chemistry-A European Journal,2017,23(62):15783-15789), in order to enable the sulfonium salt to have good absorption at long wavelengths (>350nm) , this type of sulfonium salt needs to have a larger conjugated structure, and the synthesis of this larger conjugated structure is more difficult, there are many steps and the yield is low, and the industrial production is more difficult

Method used

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  • Sulfonium salt containing pyrazoline groups and preparation method and application thereof
  • Sulfonium salt containing pyrazoline groups and preparation method and application thereof
  • Sulfonium salt containing pyrazoline groups and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0088] Embodiment 1: Synthesize the sulfonium salt (H-PAG) that target molecule contains pyrazoline group according to the following route:

[0089]

[0090] (a) Sodium hydroxide, absolute ethanol, normal temperature, 2h;

[0091] (b) Sodium hydroxide, absolute ethanol, 80°C, 5h;

[0092] (c) Methyl trifluoromethanesulfonate, dichloromethane, protected from light, room temperature, 24h; potassium hexafluorophosphate, room temperature.

[0093] 1. Synthesis of 3-(4-methylmercaptophenyl)-1-phenyl-2-en-1-one

[0094] Add acetophenone (12.02 g, 0.10 mol), 4-methylmercaptobenzaldehyde (15.22 g, 0.10 mol) and absolute ethanol (80 mL) into a 250 mL three-necked flask containing a magnetic rotor, and stir at room temperature. Then an aqueous solution of sodium hydroxide (8 g, 0.20 mol, 10 mL) was prepared and added dropwise to the reaction system through a constant pressure dropping funnel. After the addition was completed, the reaction was carried out for 2 hours, and the react...

Embodiment 2

[0106] Embodiment 2: Synthesize the sulfonium salt (CF 3 -PAG):

[0107]

[0108] (a) Sodium hydroxide, absolute ethanol, normal temperature, 2h;

[0109] (b) Sodium hydroxide, absolute ethanol, 80°C, 5h;

[0110] (c) Methyl trifluoromethanesulfonate, dichloromethane, protected from light, room temperature, 24h; potassium hexafluorophosphate, room temperature.

[0111] 1. Synthesis of 3-(4-methylmercaptophenyl)-1-(4-trifluoromethylphenyl)-2-en-1-one

[0112] The product was obtained by reacting 4-trifluoromethylacetophenone and 4-methylmercaptobenzaldehyde, the method was the same as in Example 1, and the yield was 76.4%.

[0113] 1 H NMR (400MHz, Chloroform-d) δ8.08(d, J=8.1Hz, 2H), 7.78(d, J=15.7Hz, 1H), 7.75(d, J=8.1Hz, 2H), 7.55(d , J=8.5Hz, 2H), 7.43(d, J=15.7Hz, 1H), 7.25(d, J=8.1Hz, 2H), 2.51(s, 3H).

[0114] 2. Synthesis of 1-phenyl-3-(4-trifluoromethylphenyl)-5-(4-methylmercaptophenyl)-pyrazoline

[0115] Utilize 3-(4-methylmercaptophenyl)-1-(4-trifluorometh...

Embodiment 3

[0124] Embodiment 3: Synthesize the sulfonium salt (EtO-PAG) that target molecule contains pyrazoline group according to the following route:

[0125]

[0126] (a) Sodium hydroxide, absolute ethanol, normal temperature, 2h;

[0127] (b) Sodium hydroxide, absolute ethanol, 80°C, 5h;

[0128] (c) Methyl trifluoromethanesulfonate, dichloromethane, protected from light, room temperature, 24h; potassium hexafluorophosphate, room temperature.

[0129] 1. Synthesis of 3-(4-methylmercaptophenyl)-1-(4-ethoxyphenyl)-2-en-1-one

[0130] The product was obtained by reacting 4-trifluoromethylacetophenone and 4-methylmercaptobenzaldehyde, the method was the same as in Example 1, and the yield was 76.4%.

[0131] 1 H NMR (400MHz, Chloroform-d) δ8.05(d, J=9.9Hz, 2H), 7.78(d, J=15.6Hz, 1H), 7.58(d, J=8.9Hz, 2H), 7.53(d ,J=15.6Hz,1H),7.27(d,J=8.9Hz,2H),6.99(d,J=9.9Hz,2H),4.14(q,J=7.0Hz,2H),2.54(s,3H ), 1.47 (t, J=7.0Hz, 3H).

[0132] 2. Synthesis of 1-phenyl-3-(4-ethoxyphenyl)-5-(4-met...

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Abstract

The invention provides a sulfonium salt containing pyrazoline groups and a preparation method and an application thereof, wherein the general formula of the sulfonium salt is shown in the description;R <0> and R <1> are independently selected from hydrogen, halogen atom, R', OH, OR', CH2OH, CH2OR', NR'R <0>, CH2NR'R <0>, CF3, NO2 or CN; R2 is selected from aryl groups substituted by CH2R or R4, R5, R6, R7 and R8; R3 is selected from aryl groups substituted by CH2R or R9, R10, R11, R12 and R13; the sulfonium salt is monosubstituted on the phenyl ring, and the substitution position is selectedfrom the ortho, meta or para position of the pyrazoline group; X- is selected from Cl-, CF3SO3-, CH3SO3-, BF4-, B(Ph)4-, B(PhF5)4-, PF6-, SbF6-, (CF3CF2)nPF6-n- or ((CF3)3CO) 4Al; the sulfonium salt containing the pyrazoline group can be excited by the LED, and has good light absorption and photo-acid generation properties; in addition, the preparation method has the advantages of simple process,low cost, less pollution and high yield, and can be used for industrial production.

Description

technical field [0001] The invention belongs to the technical field of new material organic chemicals, and in particular relates to a sulfonium salt containing a pyrazoline group and a preparation method and application thereof. Background technique [0002] In the early 1980s, Ito of IBM first proposed a chemically amplified resist (Ito H., Wilson C.G., Frechet J.M.S., Process of 1982 Symposium on VLSI Technology, 1982, 1:86-87). After more than 30 years of development, chemically amplified resists have been widely recognized and applied in the field of imaging materials. The chemical amplification system has become the basic choice of high-sensitivity resist. In chemically amplified resists, photoacid generators have been extensively studied. Due to the good chemical amplification effect of photoacid generators, it is not only widely used in the field of imaging materials, but also in the fields of two-dimensional and three-dimensional microlithography technology, scale ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D231/06C08F2/48
Inventor 金明陈世雄万德成樊彬吴红辉汤文杰
Owner TONGJI UNIV
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