Benzophenone-containing conjugated stilbene dye and synthesis and application thereof

Abstract

The invention discloses conjugated stilbene dye and synthesis and application thereof, belongs to the field of organic dye, and in particular relates to benzophenone-containing conjugated stilbene dye and synthesis and application thereof. A chemical structural formula is shown as (I), wherein compounds in the molecular structural formula (I) represent A:R1, R2:H, R3:CH3, OCH3, OCH2CH3, OCH2CH2CH3, OCH2CH2CH2CH3, N(CH3)2, N(CH2CH3)2, N(CH2CH2CH3)2, N(CH2CH2CH2CH3)2, CN, F, NO2; B:(R1, R2:, R3:OCH3); C:(R1:H, R2, R3: OCH3). A benzophenone-containing conjugated stilbene dye compound is synthesized by reacting 4-diethy benzophenone phosphonate and benzaldehyde derivatives in a glass container under the alkaline condition, and the maximum absorption of the benzophenone-containing conjugated stilbene dye compound is in a visible light area. The benzophenone-containing conjugated stilbene dye can be used as a photoinitiator to form a photosensitive system used for visible light polymerization of vinyl monomers in solution with an auxiliary agent triethanolamine, or can be used as a photocuring material.

Description

technical field

[0001] The invention belongs to the field of visible light initiators, in particular to a class of conjugated benzophenone-containing stilbene dyes and their synthesis and application. Background technique

[0002] In recent years, long-wavelength lasers such as Ar+ (488nm, 514nm), YAG (532nm), and He-Ne (633nm) have been widely used in computer-to-plate, photocuring, two-photon photopolymerization, and high-density digital optical storage. Efficient visible light photoinitiators have become an important field of optical information research. One approach is to attach a UV photoinitiator to a visible light dye through a chemical bond. Koichi Kawamura found that the ultraviolet photoinitiator trichloro-s-triazine attached to the visible light cyanine dye can increase the absorption light to 500-600nm. The title is: "Synthesis and evaluation of a new dye-linked bis(trichloromethyl )-1,3,5-triazine as visible light photopolymerization initiator"(Synthesis and ...

Examples

Embodiment 1

[0045] (4-(3,4-Dihydroxystyryl)phenyl)(phenyl)methanone

[0046] The synthesis proceeds in three steps:

[0047] (1) Synthesis of 4-bromomethylbenzophenone

[0048] 1.0g 4-methylbenzophenone is mixed with 0.91g N-bromosuccinimide (NBS) (molar ratio 1: 1) in a three-necked ground-necked flask, and a condensing device is added. 4 Reflux for 6 hours, filter, recrystallize the solid in benzene / cycloethane, filter to obtain crystals, the yield is 55%, and set aside;

[0049] (2) Synthesis of 4-benzophenone-phosphonic acid diethyl ester

[0050] The ratio of 2.75g 4-bromomethylbenzophenone synthesized in the first step and 16.6g triethyl phosphinate (molar ratio 1:10) was reacted at 145°C for some time, cooled, and excess phosphinate was removed under reduced pressure. Triethyl phosphonate was obtained to obtain diethyl 4-benzophenonyl phosphonate, without further purification, the yield was 86%, and it was set aside;

[0051] (3) Synthesis of (4-(3,4-dihydroxystyryl) phenyl) (p...

Embodiment 2

[0054] Synthesis of (4-(4-(diethylamino)styryl)phenyl)(phenyl)methanone

[0055] The synthesis proceeds in three steps:

[0056] (1) Synthesis of 4-bromomethylbenzophenone

[0057] Carry out in the first step according to embodiment 1;

[0058] (2) Synthesis of 4-benzophenone-phosphonic acid diethyl ester

[0059] Synthesis is carried out by the second step in the implementation case 1;

[0060] (3) Synthesis of (4-(4-(diethylamino)styryl)phenyl)(phenyl)methanone

[0061] Add 1.6 g of diethyl 4-benzophenonylphosphonate synthesized in the second step into a three-necked flask, add dry tetrahydrofuran, add a basic catalyst in an ice bath, stir magnetically for half an hour, and remove the ice bath, add 0.85g of N, N-diethylbenzaldehyde, and then stir the reaction at room temperature for 24 hours. The solvent is evaporated to dryness in a rotary evaporator, and the remaining mixture is dissolved in chloroform, washed three times with primary distilled water, and washed with c...

Embodiment 3

[0063] Synthesis of (4-(4-nitrostyryl)phenyl)(phenyl)methanone

[0064] The synthesis proceeds in three steps:

[0065] (1) Synthesis of 4-bromomethylbenzophenone

[0066] Carry out in the first step according to embodiment 1;

[0067] (2) Synthesis of 4-benzophenone-phosphonic acid diethyl ester

[0068] Synthesis is carried out by the second step in the implementation case 1;

[0069] (3) Synthesis of (4-(4-nitrostyryl) phenyl) (phenyl) ketone

[0070] Add 1.7 g of diethyl 4-benzophenonylphosphonate synthesized in the second step into a three-necked flask, add dry tetrahydrofuran, add a basic catalyst in an ice bath, stir magnetically for half an hour, and remove the ice bath, add 0.77g of N,N-diethylbenzaldehyde, and then stir the reaction at room temperature for 24 hours, the solvent is evaporated to dryness in a rotary evaporator, and the remaining mixture is dissolved in chloroform, washed three times with a single distilled water, and washed with chloroform Extract...

technical field

[0001] The invention belongs to the field of visible light initiators, in particular to a class of conjugated benzophenone-containing stilbene dyes and their synthesis and application. Background technique

[0002] In recent years, long-wavelength lasers such as Ar+ (488nm, 514nm), YAG (532nm), and He-Ne (633nm) have been widely used in computer-to-plate, photocuring, two-photon photopolymerization, and high-density digital optical storage. Efficient visible light photoinitiators have become an important field of optical information research. One approach is to attach a UV photoinitiator to a visible light dye through a chemical bond. Koichi Kawamura found that the ultraviolet photoinitiator trichloro-s-triazine attached to the visible light cyanine dye can increase the absorption light to 500-600nm. The title is: "Synthesis and evaluation of a new dye-linked bis(trichloromethyl )-1,3,5-triazine as visible light photopolymerization initiator"(Synthesis and ...

Examples

Embodiment 1

[0045] (4-(3,4-Dihydroxystyryl)phenyl)(phenyl)methanone

[0046] The synthesis proceeds in three steps:

[0047] (1) Synthesis of 4-bromomethylbenzophenone

[0048] 1.0g 4-methylbenzophenone is mixed with 0.91g N-bromosuccinimide (NBS) (molar ratio 1: 1) in a three-necked ground-necked flask, and a condensing device is added. 4 Reflux for 6 hours, filter, recrystallize the solid in benzene / cycloethane, filter to obtain crystals, the yield is 55%, and set aside;

[0049] (2) Synthesis of 4-benzophenone-phosphonic acid diethyl ester

[0050] The ratio of 2.75g 4-bromomethylbenzophenone synthesized in the first step and 16.6g triethyl phosphinate (molar ratio 1:10) was reacted at 145°C for some time, cooled, and excess phosphinate was removed under reduced pressure. Triethyl phosphonate was obtained to obtain diethyl 4-benzophenonyl phosphonate, without further purification, the yield was 86%, and it was set aside;

[0051] (3) Synthesis of (4-(3,4-dihydroxystyryl) phenyl) (p...

Embodiment 2

[0054] Synthesis of (4-(4-(diethylamino)styryl)phenyl)(phenyl)methanone

[0055] The synthesis proceeds in three steps:

[0056] (1) Synthesis of 4-bromomethylbenzophenone

[0057] Carry out in the first step according to embodiment 1;

[0058] (2) Synthesis of 4-benzophenone-phosphonic acid diethyl ester

[0059] Synthesis is carried out by the second step in the implementation case 1;

[0060] (3) Synthesis of (4-(4-(diethylamino)styryl)phenyl)(phenyl)methanone

[0061] Add 1.6 g of diethyl 4-benzophenonylphosphonate synthesized in the second step into a three-necked flask, add dry tetrahydrofuran, add a basic catalyst in an ice bath, stir magnetically for half an hour, and remove the ice bath, add 0.85g of N, N-diethylbenzaldehyde, and then stir the reaction at room temperature for 24 hours. The solvent is evaporated to dryness in a rotary evaporator, and the remaining mixture is dissolved in chloroform, washed three times with primary distilled water, and washed with c...

Embodiment 3

[0063] Synthesis of (4-(4-nitrostyryl)phenyl)(phenyl)methanone

[0064] The synthesis proceeds in three steps:

[0065] (1) Synthesis of 4-bromomethylbenzophenone

[0066] Carry out in the first step according to embodiment 1;

[0067] (2) Synthesis of 4-benzophenone-phosphonic acid diethyl ester

[0068] Synthesis is carried out by the second step in the implementation case 1;

[0069] (3) Synthesis of (4-(4-nitrostyryl) phenyl) (phenyl) ketone

[0070] Add 1.7 g of diethyl 4-benzophenonylphosphonate synthesized in the second step into a three-necked flask, add dry tetrahydrofuran, add a basic catalyst in an ice bath, stir magnetically for half an hour, and remove the ice bath, add 0.77g of N,N-diethylbenzaldehyde, and then stir the reaction at room temperature for 24 hours, the solvent is evaporated to dryness in a rotary evaporator, and the remaining mixture is dissolved in chloroform, washed three times with a single distilled water, and washed with chloroform Extract...

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