TW202136215A - A carbazole oxime ester compound, preparation method, composition and application thereof - Google Patents

Abstract

The invention discloses a carbazole oxime ester compound, a preparation method, a composition and an application thereof. The carbazole oxime ester photoinitiator has the characteristics of high sensitivity and ability to absorb long-wavelength light. On the one hand, absorbing long-wavelength light can increase deep curing. On the other hand, it can also avoid competition between other shorter-wavelength ultraviolet light absorbers and photoinitiators in the formulation. The initiation ability of the compound of the present invention in the long wavelength band is stronger than the existing carbazole oxime ester photoinitiator, and can be used alone or in combination with it.

Description

A carbazole oxime ester compound, preparation method, composition and application

The invention belongs to the technical field of photoinitiators, and specifically relates to a carbazole oxime ester compound, a preparation method, a composition and an application. The carbazole oxime ester compound of the present invention is used in photocuring, optical or electronic industries.

Photoinitiators are important chemicals in the photocuring industry, such as coatings, inks, adhesives, and photoresists. The monomer of the photocurable material must be added with a photoinitiator to be able to excite the unsaturated groups in the photocurable material to polymerize and cause the curing of the photocurable material under the irradiation of a light source of a certain wavelength. A good photoinitiator is the key to the success of photocuring technology. Traditional photoinitiators include benzoin, acetophenones, benzophenones, thioxanthones, phosphine oxides, aromatic diazonium salts, ferrocenes, triazines, hexaaryl two Imidazoles and oxime esters, etc. Among them, carbazole oxime esters are particularly valued. For example, the emergence of OXE-02 has made significant progress in the photoinitiation industry.

Generally, ultraviolet light absorbers are often added to curing formulations to protect the cured resin from degradation by light irradiation, such as Tinuvin 400 or TiO2, which absorb ultraviolet light in the range of 400 nm or higher. Or add violet and blue light absorber to the lens to protect the eyes. These ultraviolet-blue light absorbers will compete with the photoinitiator for incident light, resulting in a decrease in the initiation ability. Although the OXE-02 carbazole oxime ester photoinitiator absorbs longer wavelength light, it is still affected.

Therefore, increasing the wavelength absorbed by the existing carbazole oxime ester photoinitiators has always been the goal of the industry.

Purpose: In order to solve the shortcomings of the prior art, the present invention provides a carbazole oxime ester compound, preparation method, composition and application. On the one hand, the carbazole oxime ester photoinitiator of the present invention has a better absorption range at long wavelengths. Deep curing ability. On the other hand, the carbazole oxime ester photoinitiator of the present invention has a longer wavelength absorption range, which can prevent other ultraviolet absorbers in the formulation from competing for incident excitation light.

The compound of the present invention has better initiation ability in the long wavelength band, and can be used alone or in combination with existing carbazole oxime ester photoinitiators, such as OXE-02. Technical solution: In order to solve the above technical problems, the technical solution adopted by the present invention is as follows: In the first aspect, a compound of formula (I) or a salt thereof is provided

； R₂選自 Where R ₁ is

; R _{2 is} selected from

、

、氫、含1-20 個碳的烷基、烯基、炔基、芳基，其中，R₂和R₃至少有一個 是

； R _{3 is} selected from

,

, Hydrogen, alkyl, alkenyl, alkynyl, aryl containing 1-20 carbons, wherein at least one of _{R 2} and R _{3 is}

；

R ₄ is one or more substituents, and each is independently selected from hydrogen, hydroxy, oxy, thio, halogen, amino, nitro, nitroso, cyano, carboxy, and alkane containing 1-20 carbons. Group, alkenyl, aryl, heterocyclyl, carbonyl, acyl, alkylamino, alkoxy, alkylthio, arylalkyl, heterocyclylalkyl, arylalkenyl, heterocyclylalkenyl base;

R ₅ is one or more substituents, and each is independently selected from CN, COO R ₇ , unsubstituted or substituted phenyl _{with R 4;}

R _{6 is} selected from hydrogen, CN, COO R ₇ , unsubstituted or substituted with R ₄ phenyl, alkyl, alkenyl, alkoxy, aryl, heterocyclic group containing 1-20 carbons;

R _{7 is} selected from hydrogen, alkyl groups containing 1-20 carbons, alkenyl groups, alkoxy groups, aryl groups and heterocyclic groups;

m=1-3; n=1-3; p=0-2; q=0-1;

Preferably, m=1-2; n=1-2; p=0-1; q=0-1;

More preferably, m=1; n=1; p=0-1; q=0-1;

X=C or N;

Preferably, q=1, X=C, and R ₁ and R _{2 are} at the 3rd or 6th position of the carbazole ring.

More preferably, q=1 and R ₅ is a single substitution.

Particularly well,

Preferably, q=0, X=C, R ₁ -R _{2 are} at the 3rd or 6th position of the carbazole ring, and R ₅ is 2 substitutions.

R ₅ is one or more substituents, and each is independently selected from CN, COO R ₇ , unsubstituted or substituted phenyl _{with R 4 ; R 6 is} selected from hydrogen, unsubstituted or substituted with R ₄ phenyl, Alkyl, alkenyl, alkoxy, aryl, heterocyclic group containing 1-20 carbons;

Preferably, R _{3 is} selected from

An alkyl group of 1-18 carbons.

Preferably, R _{2 is} selected from

More preferably, R ₃ and R _{7 are} selected from alkyl groups containing 1-8 carbons; R ₄ and R _{6 are} selected from H, halogen, alkyl groups containing 1-8 carbons, alkoxy groups, and alkylamino groups.

，其中，R₇選自含的1-4個碳的烷基。 More preferably, R _{6 is} selected from CN, COOR ₇ ,

, Wherein R _{7 is} selected from alkyl groups containing 1-4 carbons.

In some embodiments, the compound of the present invention is selected from:

In the second aspect, a method for preparing the compound of formula (I) is provided, which includes:

The first synthesis method:

The second synthesis method:

The third synthesis method:

The fourth synthesis method:

From the perspective of third parties, the present invention provides a composition comprising at least one compound of formula (I), various monomers or prepolymers. The compound of formula (I) or its salt or composition can be used as a photoinitiator, light absorption, photosensitizer or photosensitizer. The composition of the present invention may include hydrogen donors, photosensitizers, or various stabilizers.

Detailed ways

The present invention will be further described below in conjunction with embodiments. The following embodiments are only used to illustrate the performance of the present invention more clearly, and are not limited to the following embodiments.

Example 1 9-Ethyl-6-isobutyryl-9H-carbazole-3-carbaldehyde (1)

Add 45g of N-ethylcarbazole-3-formaldehyde and 250ml of anhydrous dichloroethane into a 500ml four-necked flask, stir to dissolve 5, and then slowly add 58g of anhydrous aluminum trichloride. Control the temperature not to exceed 40℃, stir for 10-15 minutes, then stir and cool to about 5℃. Slowly add a solution of isobutyryl chloride in dichloroethane (consisting of 23.8g isobutyryl chloride and 20ml dichloroethane) into the reaction flask, Keep the temperature at 5-10°C, add it in 1 hour, and then keep the temperature at 5-10°C for 1 hour (HPLC tracking analysis). The reaction solution was slowly added dropwise to ice water at a temperature of 10~23°C, and then heated to 30~40°C and stirred for 0.5 hours. Separate the organic layer and wash with water to a pH of 7. Reduce pressure to dryness. Wash with ethyl acetate to obtain compound (1), melting point: 134~135°C.

Example 2 9-Ethyl-6-acetyl-9H-carbazole-3-carbaldehyde (2)

According to the method of Example 1, but replacing isobutyryl chloride with acetyl chloride, compound (2) was obtained. MS[M]+ 265.1.

Example 3 3-(9-ethyl-6-isobutyryl-9H-carbazol-3-yl)-1-phenylprop-2-en-1-one (3)

Mix 1.1g KOH, 50mL methanol, and 1.5g acetophenone, add .3g of 9-ethyl-6-isobutyryl-9H-carbazole-3-carbaldehyde, heat to reflux, react for 4h, and recover the solvent under reduced pressure. Silica gel column chromatography to obtain compound (3). MS[M] ⁺ 395.2.

Example 4 3-(9-Ethyl-6-(1-(oximino)-2-methylpropyl)-9H-carbazol-3-yl)-1-phenylprop-2-ene-1 -Ketone (4)

A 250 ml four-necked flask was charged with 8 g of compound (3), 2.0 g of hydroxylamine hydrochloride, 6.8 g of sodium acetate, and 104 g of ethanol, and the mixture was heated to reflux for 10 hours. Drain the ethanol and wash with water. It was washed with methanol, filtered, and subjected to silica gel column chromatography to obtain compound (4). MS[M] ⁺ 410.2.

The structural formula of the by-product was ^{identified as follows by 13} C-NMR. The disappearance of the C=O peak and the generation of the C=N peak (chemical shift 164.6) determine the relative value of the product and the by-product.

Example 5

3-(6-(1-(Acetoxyimino)-2-methylpropyl)-9-ethyl-9H-carbazol-3-yl)-1-phenylprop-2-ene- 1-ketone (5)

Add 2.3g of compound (10) and 50g of tetrahydrofuran to a 250ml four-necked flask, stir to dissolve, cool to 0~5℃, add 1g of triethylamine, keep the temperature at 0~5℃, add dropwise the tetrahydrofuran solution of acetyl chloride (from 0.8g acetyl chloride and 3g tetrahydrofuran), add in 10 minutes, keep 0~5 degrees and react for 3 hours. Add 5g of water, stir and hydrolyze for 10 minutes, filter, and wash the filter cake 3 times. Compound (5) is obtained. MS[M] ⁺ 452.2.

Example 6 3-(6-(1-(Acetoxyimino)-2-methylpropyl)-9-ethyl-9H-carbazol-3-yl)-1-(o-tolyl) Prop-2-en-1-one (6)

According to the method of Examples 1-5, but using o-methylacetophenone instead of acetophenone, compound (6) was obtained. MS[M] ⁺ 466.2.

Example 7 3-(6-(1-(Acetoxyimino)-2-methylpropyl)-9-ethyl-9H-carbazol-3-yl)-1-(2-chlorobenzene Base) prop-2-en-1-one (7)

According to the method of Example 1-5, but using o-chloroacetophenone instead of acetophenone, compound (7) was obtained. MS[M] ⁺ 417.2.

Example 8 3-(6-(1-(Acetoxyimino)-2-methylpropyl)-9-ethyl-9H-carbazol-3-yl)-1-(4-(二(Methylamino)phenyl)prop-2-en-1-one (8)

According to the method of Examples 1-5, but using p-dimethylaminoacetophenone instead of acetophenone, compound (8) was obtained. MS[M] ⁺ 495.3.

Example 9 3-(6-(1-(Acetoxyimino)2-methylpropyl)-9-ethyl-9H-carbazol-3-yl)-2-cyanoacrylate ethyl ( 9)

According to a similar method in Example 1-5, but using ethyl 2-cyanoacetate instead of acetophenone and piperidine instead of K OH, the reaction was carried out in ethanol at room temperature. MS[M] ⁺ 445.2.

Example 10 3-(6-(1-(Acetoxyimino)-2-methylpropyl)-9-ethyl-9H-carbazol-3-yl)-2-cyano-3- (4-(Dimethylamino)phenyl)ethyl acrylate (10)

According to the method of Example 9, but with 2-(9-ethyl-6-isobutyryl-9H-carbazol-3-yl)acetonitrile instead of 9-ethyl-6-isobutyryl-9H-carbazole-3-carbaldehyde . 4-(Dimethylamino)benzaldehyde replaces acetophenone. Compound (9) is obtained. MS[M] ⁺ 564.3.

Example 11 3-chloro-1-phenyl-1-acetone (11)

Add 100 mL of hydrochloric acid (4M, in dioxane solution) to the pre-cooled 1-phenyl-prop-2-en-1-one (7g) in CH ₂ Cl ₂ (200 mL) solution, which has already reacted The mixture was stirred at 0°C for 1 hour, and concentrated under reduced pressure to obtain compound (11), mp=48°C.

Example 12 9-((3-oxo-3-phenylpropyl)-9H-carbazole-3,6-diyl) bis(ethane-1-one) (12)

Acetate 9H-carbazole to obtain 1,1'-(9H-carbazole-3,6-diyl)bis(ethane-1-one), mp=251ºC. Take 20g of 1,1'-(9H-carbazole-3,6-diyl)bis(ethane-1-one) and 66g of potassium carbonate and add to the flask, add DMF to become turbid. 60 g of compound (10) was slowly added to the reaction mixture, and heated and stirred at 80° C. overnight. 200 mL of ethyl acetate was added to the reaction mixture, and then filtered to remove inorganic salts. Compound (12) is obtained. MS[M] ⁺ 383.2.

Example 13 3-(9H-carbazol-9-yl)-1-phenylprop-2-en-1-one (13)

2 g of palladium acetate was suspended in 100 ml of acetonitrile, 1.6 g of triethylamine, 3 g of compound (12) were added, and the mixture was heated to reflux under nitrogen for 1 hr. The catalyst is filtered, concentrated, washed with water and dried to obtain compound (13). MS[M] ⁺ 381.1.

Example 14 ((9-(3-oxo-3-phenylprop-1-en-1-yl)-9H-carbazole-3,6-diyl)bis(acetaldehyde O-acetyloxime )(14)

According to the methods of Examples 4 and 5, but using compound (13) instead of compound (4), compound (14) was obtained. MS[M] ⁺ 495.2.

Example 15 ((9-(3-oxo-3-o-methylphenylprop-1-en-1-yl)-9H-carbazole-3,6-diyl)bis(acetaldehyde O-ethyl Oxime) (15)

According to the method of Examples 11-14, but replacing 1-phenyl-prop-2-en-1-one with 1-o-methylphenyl-prop-2-en-1-one. Compound (15) is obtained. MS[M] ⁺ 509.2.

Example 16 ((9-(3-oxo-3-o-chlorophenylprop-1-en-1-yl)-9H-carbazole-3,6-diyl)bis(acetaldehyde O-acetaldehyde Base oxime) (16)

According to the method of Examples 11-14, but using 1-o-chlorophenyl-prop-2-en-1-one instead of 1-phenyl-prop-2-en-1-one. Compound (16) is obtained. MS[M] ⁺ 529.1.

Example 17 ((9-(3-oxo-3-p-cyanophenylprop-1-en-1-yl)-9H-carbazol-3,6-diyl)bis(acetaldehyde O- Acetyl oxime) (17)

According to the method of Examples 11-14, but with 1-p-cyanophenyl-prop-2-en-1-one (mp=53ºC) instead of 1-phenyl-prop-2-en-1-one. Compound (17) is obtained. MS[M] ⁺ 520.2.

Example 18 ((9-(3-oxo-3-p-nitrophenylprop-1-en-1-yl)-9H-carbazole-3,6-diyl)bis(acetaldehyde O-ethyl Oxime) (18)

According to the method of Examples 11-14, but with p-cyanophenyl-prop-2-en-1-one (mp=81ºC) instead of 1-phenyl-prop-2-en-1-one. Compound (18) is obtained. MS[M] ⁺ 540.2.

Example 19 ((9-(3-oxo-3-p-methoxyphenylprop-1-en-1-yl)-9H-carbazole-3,6-diyl)bis(acetaldehyde O- Acetyl oxime) (19)

According to the method of Examples 11-14, but with 1-p-methoxyphenyl-prop-2-en-1-one (mp=20ºC) instead of 1-phenyl-prop-2-en-1-one. Compound (19) is obtained. MS[M] ⁺ 525.2

Example 20 (9-(3-oxo-3-p-decyloxyphenylprop-1-en-1-yl)-9H-carbazole-3,6-diyl)bis(acetaldehyde O-ethyl Oxime) (20)

According to the method of Examples 11-14, but with 1-p-decyloxyphenyl-prop-2-en-1-one (mp=36ºC) instead of 1-phenyl-prop-2-en-1-one. Compound (20) is obtained. MS[M] ⁺ 651.3.

Example 21 (9-(3-oxo-3-(2-methyl-4-methoxyphenyl)prop-1-en-1-yl)-9H-carbazole-3,6-diyl ) Bis (acetaldehyde O-acetoxy oxime) (21)

According to the method of Examples 11-14, but using 2-methyl-4-methoxyphenyl-2-en-1-one instead of 1-phenyl-prop-2-en-1-one. Compound (20) is obtained. MS[M] ⁺ 539.2.

Example 22 (9-(3-oxo-3-(p-2-methylaminophenyl)prop-1-en-1-yl)-9H-carbazole-3,6-diyl)bis( Acetaldehyde (O-acetyl oxime) (22)

According to the method of Examples 11-14, but using p-dimethylaminophenyl-2-en-1-one instead of 1-phenyl-prop-2-en-1-one, compound (22) was obtained. MS[M] ⁺ 538.2.

Example 23 (9-(3-oxo-3-(p-hydroxyphenyl)prop-1-en-1-yl)-9H-carbazole-3,6-diyl)bis(acetaldehyde O-ethyl Oxime) (23)

According to the method of Examples 11-14, but using p-hydroxyphenyl-2-en-1-one instead of 1-phenyl-prop-2-en-1-one, compound (23) was obtained. MS[M] ⁺ 511.2.

Example 24 1-(9H-carbazol-9-yl)-N-phenylanimine (24)

6.5g of aniline was dissolved in 40ml of tetrahydrofuran, and the temperature was raised to 40-50°C. 20g carbazole formaldehyde (mp=98ºC), dissolve in 40ml tetrahydrofuran, stir to dissolve at room temperature. Add the carbazole formaldehyde solution dropwise to the aniline solution. Add 6mL of acetic acid and reflux for 18-24h. The solvent was evaporated and column chromatography was used to obtain compound (24). MS[M] ⁺ 270.1.

Example 25 9-((phenylimino)methyl)-9H-carbazole-3,6-diyl)bis(ethane-1-one) (25)

27 grams of compound (24) and 26.4 grams of aluminum chloride were mixed _{in CH 2} Cl _2. In an ice bath, slowly add 19 mL of acetyl chloride. Stir and monitor the reaction. After the reaction is complete, pour it into 1L of crushed ice. The organic phase was separated, and the aqueous phase was extracted with 120 mL of CH ₂ Cl ₂ . The combined organic phase was washed with 120 ml of water and then with 120 ml of saturated aqueous sodium bicarbonate solution. Dry with Na ₂ SO ₄ and filter. Compound (25) is obtained. MS[M] ⁺ 354.1.

by-product:. According to the method of Example 4-5, but substituting Compound (25.1) for Compound (3), Compound (25.2) was obtained.

Example 26 9-((Phenylimino)methyl)-9H-carbazole-3,6-diyl-bis(ethan-1-one)O,O-diethyl dioxime (26)

According to the method of Example 4-5, but using compound (25) instead of compound (3). Compound (26) is obtained. MS[M] ⁺ 468.2 .

Example 27 Ethyl 4-(((3,6-bis(1-(acetoxyimino)ethyl)-9H-carbazol-9-yl)methylene)amino)benzoate (27)

According to the method of Examples 24-26, but using ethyl 4-aminobenzoate instead of aniline, compound (27) was obtained. MS[M] ⁺ 540.2.

Example 28 4-(((3,6-bis(1-(acetoxyimino)ethyl)-9H-carbazol-9-yl)methylene)amino) octyl benzoate (28)

According to the method of Examples 24-26, but using octyl 4-aminobenzoate (mp=68ºC) instead of aniline, compound (28) was obtained. MS[M] ⁺ 624.3.

Example 29 Ethyl 4-(((3,6-bis(1-(phenoxyimino)ethyl)-9H-carbazol-9-yl)methylene)amino)benzoate (29)

According to the method of Examples 24-26, but using phenacyl chloride instead of acetyl chloride, compound (29) was obtained. MS[M] ⁺ 664.2.

Example 30 (9-(((4-(dimethylamino)phenyl)imino)methyl)-9H-carbazole-3,6-diyl)bis(ethane-1)-one)O , O-Diacetyl dioxime (30)

According to the method of Examples 24-26, but using N1,N1-xylene-1,4-diamine instead of aniline, compound (30) was obtained. MS[M] ⁺ 511.2.

Example 31

The pre-polymerized composition includes 0.05% of photoinitiator (control OXE-02 compound or example compound), 0.5 mL of methyl methacrylate. Add or not add the anti-blue light agent Eusorb 1990 to the sample. And by purging with nitrogen to remove oxygen. Polymerize with 420-450nm light. After the polymerization is completed, the remaining monomers are evaporated, and the remaining solids are weighed. The more remaining weight, the stronger the polymerization ability of the photoinitiator. Test results in Table 1. The + sign indicates the initiation ability of the photoinitiator, and the more the + sign indicates the stronger the initiation ability of the photoinitiator.

Table 1 Test results

The results show that the compound of the examples above 420nm, used alone or in combination with OXE-02, has stronger initiation ability than OXE-02.

The present invention has been disclosed in preferred embodiments above, but it is not intended to limit the present invention. It is clear that all technical solutions obtained by equivalent replacement or equivalent transformation methods fall within the protection scope of the present invention.

Claims (10)

A compound of formula (I) or a salt thereof,

in, R ₁ is

； R _{2 is} selected from

R _{3 is} selected from

,

, Hydrogen, alkyl, alkenyl, alkynyl, aryl containing 1-20 carbons, wherein at least one of _{R 2} and R _{3 is}

； R ₄ is one or more substituents, and each is independently selected from hydrogen, hydroxy, oxy, thio, halogen, amino, nitro, nitroso, cyano, carboxy, and alkane containing 1-20 carbons. Group, alkenyl group, aryl group, carbonyl group, acyl group, ester group, alkylamino group, alkoxy group, alkylthio group; R ₅ is one or more substituents, and each is independently selected from CN, COO R ₇ , and R ₄ substituted phenyl groups; R _{6 is} selected from hydrogen, CN, COO R ₇ , _{phenyl substituted with R 4} , alkyl, alkenyl, alkoxy, and aryl groups containing 1-20 carbons; R _{7 is} selected from hydrogen, alkyl groups containing 1-20 carbons, alkenyl groups, alkoxy groups, and aryl groups; m=1 or 2; n=1 or 2; p=0, 1 or 2; q=0 or 1; X=C or N. The compound according to claim 1, characterized in that, m = 1, n = 1 , p = 0 or 1, R ₄ is hydrogen. The compound of claim 2, wherein R ₁ and R _{2 are} at the 3rd or 6th position of the carbazole ring. The compound of claim 3, wherein R ₁ is

R ₂ is

； R _{3 is} selected from

,

, 1-18 carbon alkyl group. The compound of claim 4, wherein R _{2 is} selected from

The compound according to claim 4, wherein R ₃ and R _{7 are} selected from alkyl groups containing 1-8 carbons; R ₄ and R _{6 are} selected from H, alkyl groups containing 1-8 carbons, and alkyl groups containing 1-8 carbons. Oxy group, alkylamino group. The compound according to claim 5, wherein R _{6 is} selected from H, alkyl containing 1-6 carbons, CN, COOR ₇ ,

, Wherein R _{7 is} selected from alkyl groups containing 1-4 carbons. The compound according to claim 1, characterized in that it is selected from:

A method for preparing a compound represented by formula (I), which is characterized in that it comprises:

Wherein, R ₁ , R ₂ , R ₃ , R ₄ and R _{5 are} as defined in claim 1. A composition comprising at least one compound of formula (I) according to any one of claims 1-8 or a salt thereof.