Summary of the invention
The objective of the invention is comparatively submissive ether is incorporated in the Hexaarylbiimidazole, the consistency of preparing a class and esters of acrylic acid polymer system better and have good uv absorption property and the light-initiated active ether hexaaryl diimidazole that contains is widened the range of application of Hexaarylbiimidazole as light trigger.
The chemical structural formula of photoinitiator containing ether hexaaryl diimidazole of the present invention is shown below:
Wherein, R
1, R
2And R
3Independently be selected from hydrogen or halogen respectively; R
4For
M=1~3 wherein.
It is as follows that the present invention prepares the entire reaction equation of photoinitiator containing ether hexaaryl diimidazole:
Wherein, R
1, R
2And R
3Independently be selected from hydrogen or halogen respectively; R
4For
M=1~3 wherein.
The preparation method of photoinitiator containing ether hexaaryl diimidazole of the present invention following (following all represent) with mass parts:
(a) hydrolysis reaction: with 1 part 3,3 '-benzil of dimethoxy is dissolved in 5~15 parts the Glacial acetic acid, refluxed 30~60 minutes down at 80~100 ℃, add 5~10 parts Hydrogen bromide then, refluxed 72~84 hours down at 100~120 ℃, Glacial acetic acid and excessive Hydrogen bromide are removed in evaporation, the ethyl acetate that adds 5~20 parts is then used distilled water wash three times, with anhydrous sodium sulfate drying after-filtration evaporate to dryness, behind the dehydrated alcohol recrystallization, promptly get 3,3 '-the dihydroxyl benzil;
(b) epoxidation reaction: under nitrogen protection, with 1 part 3,3 '-the dihydroxyl benzil is dissolved in 5~15 parts the organic solvent, adds 2~10 parts Anhydrous potassium carbonate powder, stirred 30~60 minutes down at 60~100 ℃; Add 0.1~0.5 part polyoxyethylene glycol and 2~10 parts epoxy chloropropane then, refluxed 3~6 hours down at 80~100 ℃, and then under 120~140 ℃, refluxed 6~12 hours, cooled and filtered tells organic phase and organic solvent and remaining epoxy chloropropane are removed in evaporation, the ethyl acetate that adds 5-20 part then, through the 5wt% aqueous sodium hydroxide washes wash with anhydrous sodium sulfate drying after, pour in the long-pending sherwood oil of decaploid and precipitate, filter after the dehydrated alcohol recrystallization promptly get 3,3 '-the bicyclic oxygen benzil;
(c) ring-opening reaction: with 1 part 3,3 '-the bicyclic oxygen benzil is dissolved in 5~15 parts the organic solvent, add 0.5~2 part Lithium perchlorate anhydrous and many ethylene glycol monoethyl ethers of 2~10 parts, refluxed 12~24 hours down at 100~120 ℃, after the cooling with organic phase with distilled water wash three times, behind anhydrous sodium sulfate drying, pour in the long-pending sherwood oil of decaploid and precipitate, obtain 3,3 '-two ether benzils;
(d) cyclization: under protection of nitrogen gas, with 1 part 3, the mixture of the Glacial acetic acid of 3 '-two ether benzils, 0.5~2 part substituted benzaldehyde, 1~5 part ammonium acetate and 10~20 parts refluxed 12~24 hours down at 100~120 ℃, after the cooling reactant poured in 2~5wt% aqueous solution of sodium bisulfite of 50~100 parts, filter promptly to get and contain ether triaryl list imidazoles;
(e) oxidative coupling: with 1 part contain in the organic solvent that ether triaryl list imidazoles is dissolved in 5~15 parts, slowly be added drop-wise to then 0.2~2 part tetra-n-butyl ammonium bromide is housed, in the flask of the 40wt% aqueous sodium hydroxide solution of 2~5 parts the Tripotassium iron hexacyanide and 5~10 parts, refluxed 6~24 hours down at 20~60 ℃, the cooling back adds 10~50 parts distilled water, behind distilled water wash, use anhydrous sodium sulfate drying by the organic phase that organic solvent extraction obtains, organic phase after the evaporation concentration poured in the long-pending sherwood oil of decaploid precipitate, filter and contain ether hexaaryl diimidazole after first alcohol and water recrystallization promptly gets.
The number-average molecular weight of polyoxyethylene glycol used in the present invention is 400~2000.
The structural formula of many ethylene glycol monoethyl ethers used in the present invention is as follows:
Wherein, m=1~3.
The structural formula of substituted benzaldehyde used in the present invention is as follows:
Wherein, R
1, R
2, R
3Independently be selected from hydrogen or halogen respectively.
The organic solvent that the present invention uses comprises: pimelinketone, toluene, 1,4-dioxane, methylene dichloride or trichloromethane.
The present invention is incorporated into comparatively submissive ether in the Hexaarylbiimidazole, the consistency of preparing a class and esters of acrylic acid polymer system better and have good uv absorption property and the light-initiated active ether hexaaryl diimidazole that contains has extensive studies potentiality and application prospect at microelectronics such as photo-resist, printed circuit plates.Light-initiated The performance test results shows that the photoinitiator containing ether hexaaryl diimidazole of the present invention's preparation has good light-initiated activity.
The method that the present invention's test contains the light-initiated performance of ether hexaaryl diimidazole is as follows:
The toluene solution and the toluene that at first will contain ether hexaaryl diimidazole, 2-mercaptobenzoxazole, polypropyleneglycol diacrylate, polymethylmethacrylate are mixed with solution according to following table; uniform coating is on the PET film then; take by weighing the about 2.0mg of dry film after the drying, utilize the equation of light to show that scanning calorimeter (photo-DSC) utilizes 365nm light source 25 ℃ under the irradiation 3min of light intensity for 50mw under the 50ml/min nitrogen protection.
Component |
Weight (g) |
2,2 '-two (2-chloro-phenyl-)-4,4 ', 5,5 '-four [3-(2-hydroxyl-3-ethylene glycol ethyl ethers ether-propane-1-oxygen base)-phenyl]-1,2 '-diimidazole |
0.396 |
The 2-mercaptobenzoxazole |
0.092 |
Polypropyleneglycol diacrylate |
4.0 |
The toluene solution of polymethylmethacrylate |
10.0 |
Toluene |
3.0 |
The number-average molecular weight that the present invention's test contains the light-initiated performance polypropylene glycol herein of ether hexaaryl diimidazole diacrylate is 540.
The number-average molecular weight that the present invention's test contains the used polymethylmethacrylate of the light-initiated performance of ether hexaaryl diimidazole is 94,000, and the solid content of its toluene solution is 40%.
Concrete embodiment
Following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1:
(a) 3,3 of 10g '-benzil of dimethoxy is dissolved in the Glacial acetic acid of 100g, refluxed 30 minutes down at 85 ℃, the Hydrogen bromide that adds 100g then refluxed 72 hours down at 120 ℃, and Glacial acetic acid and excessive Hydrogen bromide are removed in evaporation, the ethyl acetate that adds 100g then, with distilled water wash three times,, behind the dehydrated alcohol recrystallization, promptly get 5.8g3 with anhydrous sodium sulfate drying after-filtration evaporate to dryness, 3 '-dihydroxyl benzil white crystal, yield is 64%, and fusing point is 128~132 ℃
1H NMR (DMSO-d6,400MHz, ppm): 10.07 (s, 2H, 2-OH), 7.43~7.12 (m, 8H, phenyl), FTIR (KBr, cm
-1): 3380 (s, v
O-H), 1670 (s, v
C=O);
(b) under nitrogen protection, 3,3 of 5g '-dihydroxyl benzil is dissolved in the toluene of 50g, add the Anhydrous potassium carbonate powder of 15g, stirred 60 minutes down at 80 ℃; Add the polyoxyethylene glycol of 0.2g and the epoxy chloropropane of 5g then, refluxed 3 hours down at 80 ℃, and then under 120 ℃, refluxed 12 hours, cooled and filtered tells organic phase and toluene and remaining epoxy chloropropane are removed in evaporation, the ethyl acetate that adds 50g then, through the 5wt% aqueous sodium hydroxide washes wash with anhydrous sodium sulfate drying after, pour in the long-pending sherwood oil of decaploid and precipitate, filter after the dehydrated alcohol recrystallization promptly gets 4.6g3,3 '-bicyclic oxygen benzil white crystal, yield is 63%, and fusing point is 70~72 ℃
1H NMR (DMSO-d6,400MHz, ppm): 7.54~7.38 (m, 8H, phenyl), 4.45,3.90 (m, 4H, 2-CH
2O-), 3.32 (m, 2H, 2-OCH<), 2.83,2.71 (m, 4H, 2-OCH
2-); FTIR (KBr, cm
-1): 2975 (m, v
C-H), 1670 (s, v
C=O), 1250 (vas
C-O-C), 910 (m, vsy
C-O-C);
(c) with 3 of 3g, 3 '-the bicyclic oxygen benzil is dissolved in the pimelinketone of 45g, add the Lithium perchlorate anhydrous of 1.5g and the ethylene glycol monoethyl ether of 6g, refluxed 12 hours down at 120 ℃, with organic phase distilled water wash three times, behind anhydrous sodium sulfate drying, pour in the long-pending sherwood oil of decaploid and precipitate after the cooling, obtain 2.9g3, the red oily liquids of 3 '-two [3-(2-hydroxyl-3-ethylene glycol ethyl ethers ether-propane-1-oxygen base)]-benzils, yield is 64%
1H NMR (DMSO-d6,400MHz, ppm): 7.60~7.12 (m, 8H, phenyl), 4.10~3.82 (m, 4H, the 2-CH that link to each other with phenyl
2O-), 3.60~3.30 (s, 18H, 2-OCH<and 8-CH
2O-), 1.08 (m, 6H, 2-CH
3), (KBr salt sheet is filmed cm to FTIR
-1): 3379 (s, v
O-H), 2880 (m, v
C-H), 1670 (s, v
C=O);
(d) under protection of nitrogen gas; with 3 of 2g; 3 '-two [3-(2-hydroxyl-3-ethylene glycol ethyl ethers ether-propane-1-oxygen base)]-benzils; the 2-chlorobenzaldehyde of 1g; the mixture of the ammonium acetate of 2g and the Glacial acetic acid of 20g refluxed 12 hours down at 120 ℃; after the cooling reactant is poured in the 2wt% aqueous solution of sodium bisulfite of 100g; filter and promptly get 2.1g2-(2-chloro-phenyl-)-4; 5-two [3-(2-hydroxyl-3-ethylene glycol ethyl ethers ether-propane-1-oxygen base)-phenyl]-imidazoles white powder; yield is 86%; fusing point is 60~64 ℃
1H NMR (DMSO-d6,400MHz, ppm): 12.76 (s, 1H, N-H), 7.56~7.10 (m, 12H, phenyl), 4.10~3.82 (m, 4H, the 2-CH that link to each other with phenyl
2O-), 3.60~3.30 (s, 18H, 2-OCH<and 8-CH
2O-), 1.08 (m, 6H, 2-CH
3); FTIR (KBr, cm
-1): 3375 (m, v
O-H), 3250 (m, v
N-H), 2975 (m, v
C-H), 1602 (s, v
C=C);
(e) with the 2-(2-chloro-phenyl-)-4 of 2g, 5-two [3-(2-hydroxyl-3-ethylene glycol ethyl ethers ether-propane-1-oxygen base)-phenyl]-imidazoles is dissolved in the methylene dichloride of 10g, slowly be added drop-wise to the tetra-n-butyl ammonium bromide that 0.4g is housed then, in the flask of the 40wt% aqueous sodium hydroxide solution of the Tripotassium iron hexacyanide of 5g and 10g, refluxed 12 hours down at 20 ℃, the cooling back adds the distilled water of 50g, behind distilled water wash, use anhydrous sodium sulfate drying by the organic phase that dichloromethane extraction obtains, organic phase after the evaporation concentration poured in the long-pending sherwood oil of decaploid precipitate, filter after first alcohol and water recrystallization promptly gets 1.2g2,2 '-two (2-chloro-phenyl-s)-4,4 ', 5,5 '-four [3-(2-hydroxyl-3-ethylene glycol ethyl ethers ether-propane-1-oxygen base)-phenyl]-1,2 '-diimidazole (BCTE-HABI) pale yellow crystals, yield is 58%, fusing point is 90~94 ℃, Fig. 1 is 2,2 '-two (2-chloro-phenyl-s)-4,4 ', 5,5 '-four [3-(2-hydroxyl-3-ethylene glycol ethyl ethers ether-propane-1-oxygen base)-phenyl]-1, the hydrogen nuclear magnetic resonance spectrogram of 2 '-diimidazole (promptly containing m=1 in the ether hexaaryl diimidazole chemical structural formula)
1H NMR (DMSO-d6,400MHz, ppm): 7.56~7.11 (m, 24H, phenyl), 4.10~3.82 (m, 8H, the 4-CH that link to each other with phenyl
2O-), 3.60~3.30 (s, 36H, 4-OCH<and 16-CH
2O), 1.08 (m, 12H, 4-CH
3), Fig. 2 is 2,2 '-two (2-chloro-phenyl-)-4,4 ', 5,5 '-four [3-(2-hydroxyl-3-ethylene glycol ethyl ethers ether-propane-1-oxygen base)-phenyl]-1, the infrared spectrogram of 2 '-diimidazole, FTIR (KBr, cm
-1): 3375 (m, v
O-H), 2975 (s, v
Methyl C-H), 2870 (s, v
Methylene radical C-H), 1605 (s, v
C=C), Fig. 3 is 2,2 '-two (2-chloro-phenyl-s)-4,4 ', 5,5 '-four [3-(2-hydroxyl-3-ethylene glycol ethyl ethers ether-propane-1-oxygen base)-phenyl]-1, the mass spectrum of 2 '-diimidazole (substance assistant laser desorpted attached flight time mass spectrum figure) figure, MALDI-TOF-MS:m/e 1309 (M+1), Fig. 4 is 2,2 '-two (2-chloro-phenyl-s)-4,4 ', 5,5 '-four [3-(2-hydroxyl-3-ethylene glycol ethyl ethers ether-propane-1-oxygen base)-phenyl]-1, the uv absorption spectra of 2 '-diimidazole, wherein, 2,2 '-two (2-chloro-phenyl-)-4,4 ', 5,5 '-four [3-(2-hydroxyl-3-ethylene glycol ethyl ethers ether-propane-1-oxygen base)-phenyl]-1,2 '-diimidazole is dissolved in the ethanol, and concentration is 1.0 * 10
-5Mol/l, (molar absorption coefficient of λ=365nm) locate is ε at present industrial photocuring light source the most commonly used for it
365nm=2210mol
-1Lcm
-1Fig. 5 be the method that adopts the present invention's test to contain the light-initiated performance of ether hexaaryl diimidazole obtain 2,2 '-two (2-chloro-phenyl-s)-4,4 ', 5,5 '-four [3-(2-hydroxyl-3-ethylene glycol ethyl ethers ether-propane-1-oxygen base)-phenyl]-1,2 '-diimidazole cause the photopolymerisable equation of light of polypropyleneglycol diacrylate and show scanning calorimeter test pattern, R
Pmax=0.0994s
-1, Δ H
Always=150mJ/mg, C
Always=99.14%, as seen from Figure 5,2,2 '-two (2-chloro-phenyl-)-4,4 ', 5,5 '-four [3-(2-hydroxyl-3-ethylene glycol ethyl ethers ether-propane-1-oxygen base)-phenyl]-1,2 '-diimidazole has good light-initiated activity to acrylatcs systems.
Embodiment 2:
(a) 3,3 of 10g '-benzil of dimethoxy is dissolved in the Glacial acetic acid of 50g, refluxed 30 minutes down at 100 ℃, the Hydrogen bromide that adds 50g then refluxed 78 hours down at 120 ℃, and Glacial acetic acid and excessive Hydrogen bromide are removed in evaporation, the ethyl acetate that adds 50g then, with distilled water wash three times,, behind the dehydrated alcohol recrystallization, promptly get 6.0g3 with anhydrous sodium sulfate drying after-filtration evaporate to dryness, 3 '-dihydroxyl benzil white crystal, yield is 67%, and fusing point is 128~132 ℃
1H NMR (DMSO-d6,400MHz, ppm): 10.07 (s, 2H, 2-OH), 7.43~7.12 (m, 8H, phenyl), FTIR (KBr, cm
-1): 3380 (s, v
O-H), 1670 (s, v
C=O);
(b) under nitrogen protection, 3,3 of 5g '-dihydroxyl benzil is dissolved in the pimelinketone of 50g, add the Anhydrous potassium carbonate powder of 25g, stirred 45 minutes down at 90 ℃; Add the polyoxyethylene glycol of 1.0g and the epoxy chloropropane of 15g then, refluxed 6 hours down at 85 ℃, and then under 120 ℃, refluxed 6 hours, cooled and filtered tells organic phase and toluene and remaining epoxy chloropropane are removed in evaporation, the ethyl acetate that adds 50g then, through the 5wt% aqueous sodium hydroxide washes wash with anhydrous sodium sulfate drying after, pour in the long-pending sherwood oil of decaploid and precipitate, filter after the dehydrated alcohol recrystallization promptly gets 4.5g3,3 '-bicyclic oxygen benzil white crystal, yield is 61%, and fusing point is 70~72 ℃
1H NMR (DMSO-d6,400MHz, ppm): 7.54~7.38 (m, 8H, phenyl), 4.45,3.90 (m, 4H, 2-CH2O-), 3.32 (m, 2H, 2-OCH<), 2.83,2.71 (m, 4H, 2-OCH2-); FTIR (KBr, cm
-1): 2975 (m, v
C-H), 1670 (s, v
C=O), 1250 (vas
C-O-C), 910 (m, vsy
C-O-C);
(c) with 3 of 3g, 3 '-the bicyclic oxygen benzil is dissolved in 1 of 30g, in the 4-dioxane, add the Lithium perchlorate anhydrous of 3g and the diethylene glycol monoethyl ether of 15g, refluxed 24 hours down at 100 ℃, after the cooling with organic phase with distilled water wash three times, behind anhydrous sodium sulfate drying, pour in the long-pending sherwood oil of decaploid and precipitate, obtain 3.3g3, the red oily liquids of 3 '-two [3-(2-hydroxyl-3-diethylene glycol ether base-propane-1-oxygen base)]-benzils, yield is 63%
1HNMR (DMSO-d6,400MHz, ppm): 7.60~7.12 (m, 8H, phenyl), 4.10~3.82 (m, 4H, the 2-CH that link to each other with phenyl
2O-), 3.60~3.30 (s, 26H, 2-OCH<and 12-CH
2O-), 1.08 (m, 6H, 2-CH
3), (KBr salt sheet is filmed cm to FTIR
-1): 3375 (s, v
O-H), 2880 (m, v
C-H), 1670 (s, v
C=O);
(d) under protection of nitrogen gas; with 3 of 3g; 3 '-two [3-(2-hydroxyl-3-diethylene glycol ether base-propane-1-oxygen base)]-benzils; the 2-chloro-4-fluoro-phenyl aldehyde of 6g; 7.5g ammonium acetate and the mixture of the Glacial acetic acid of 45g refluxed 24 hours down at 100 ℃; after the cooling reactant is poured in the 5wt% aqueous solution of sodium bisulfite of 220g; filter and promptly get 3.0g2-(2-chloro-4-fluoro-phenyl)-4; 5-two [3-(2-hydroxyl-3-diethylene glycol ether base-propane-1-oxygen base)-phenyl]-imidazoles white powder; yield is 82%; fusing point is 58~63 ℃
1H NMR (DMSO-d6,400MHz, ppm): 12.76 (s, 1H, N-H), 7.56~7.10 (m, 11H, phenyl), 4.10~3.82 (m, 4H, the 2-CH that link to each other with phenyl
2O-), 3.60~3.30 (s, 26H, 2-OCH<and 12-CH
2O-), 1.08 (m, 6H, 2-CH
3); FTIR (KBr, cm
-1): 3375 (m, v
O-H), 3250 (m, v
N-H), 2975 (m, v
C-H), 1605 (s, v
C=C);
(e) with the 2-(2-chloro-4-fluoro-phenyl)-4 of 2g, 5-two [3-(2-hydroxyl-3-diethylene glycol ether base-propane-1-oxygen base)-phenyl]-imidazoles is dissolved in the trichloromethane of 20g, slowly be added drop-wise to the tetra-n-butyl ammonium bromide that 3g is housed then, in the flask of the 40wt% aqueous sodium hydroxide solution of the Tripotassium iron hexacyanide of 8g and 16g, refluxed 20 hours down at 30 ℃, the cooling back adds the distilled water of 100g, behind distilled water wash, use anhydrous sodium sulfate drying by the organic phase that chloroform extraction obtains, organic phase after the evaporation concentration poured in the long-pending sherwood oil of decaploid precipitate, filter after first alcohol and water recrystallization promptly gets 1.0g2,2 '-two (2-chloro-4-fluoro-phenyl)-4,4 ', 5,5 '-four [3-(2-hydroxyl-3-diethylene glycol ether base-propane-1-oxygen base)-phenyl]-1,2 '-diimidazole pale yellow crystals, yield is 52%, and fusing point is 84~88 ℃
1H NMR (DMSO-d6,400MHz, ppm): 7.56~7.11 (m, 22H, phenyl), 4.10~3.82 (m, 8H, the 4-CH that link to each other with phenyl
2O-), 3.60~3.30 (s, 52H, 4-OCH<and 24-CH
2O), 1.08 (m, 12H, 4-CH
3), FTIR (KBr, cm
-1): 3375 (m, v
O-H), 2975 (s, v
Methyl C-H), 2872 (s, v
Methylene radical C-H), 1604 (s, v
C=C), MALDI-TOF-MS:m/e 1521 (M+1).
Embodiment 3:
(a) 3,3 of 10g '-benzil of dimethoxy is dissolved in the Glacial acetic acid of 150g, refluxed 60 minutes down at 100 ℃, the Hydrogen bromide that adds 100g then refluxed 84 hours down at 120 ℃, and Glacial acetic acid and excessive Hydrogen bromide are removed in evaporation, the ethyl acetate that adds 200g then, with distilled water wash three times,, behind the dehydrated alcohol recrystallization, promptly get 5.8g3 with anhydrous sodium sulfate drying after-filtration evaporate to dryness, 3 '-dihydroxyl benzil white crystal, yield is 65%, and fusing point is 128~132 ℃
1H NMR (DMSO-d6,400MHz, ppm): 10.07 (s, 2H, 2-OH), 7.43~7.12 (m, 8H, phenyl), FTIR (KBr, cm
-1): 3380 (s, v
O-H), 1670 (s, v
C=O);
(b) under nitrogen protection, 3,3 of 5g '-dihydroxyl benzil is dissolved in the pimelinketone of 75g, add the Anhydrous potassium carbonate powder of 50g, stirred 45 minutes down at 100 ℃; Add the polyoxyethylene glycol of 2.5g and the epoxy chloropropane of 50g then, refluxed 3 hours down at 100 ℃, and then under 140 ℃, refluxed 6 hours, cooled and filtered tells organic phase and toluene and remaining epoxy chloropropane are removed in evaporation, the ethyl acetate that adds 100g then, through the 5wt% aqueous sodium hydroxide washes wash with anhydrous sodium sulfate drying after, pour in the long-pending sherwood oil of decaploid and precipitate, filter after the dehydrated alcohol recrystallization promptly gets 4.8g3,3 '-bicyclic oxygen benzil white crystal, yield is 65%, and fusing point is 70~72 ℃
1H NMR (DMSO-d6,400MHz, ppm): 7.54~7.38 (m, 8H, phenyl), 4.45,3.90 (m, 4H, 2-CH
2O-), 3.32 (m, 2H, 2-OCH<), 2.83,2.71 (m, 4H, 2-OCH
2-); FTIR (KBr, cm
-1): 2975 (m, v
C-H), 1670 (s, v
C=O), 1250 (vas
C-O-C), 910 (m, v
SyC-O-C);
(c) with 3 of 3g, 3 '-the bicyclic oxygen benzil is dissolved in the pimelinketone of 15g, add the Lithium perchlorate anhydrous of 6g and the Triethylene glycol ethyl ether of 30g, refluxed 24 hours down at 120 ℃, with organic phase distilled water wash three times, behind anhydrous sodium sulfate drying, pour in the long-pending sherwood oil of decaploid and precipitate after the cooling, obtain 3.6g3, the red oily liquids of 3 '-two [3-(2-hydroxyl-3-tri ethylene glycol ethyl ether base-propane-1-oxygen base)]-benzils, yield is 60%
1H NMR (DMSO-d6,400MHz, ppm): 7.60~7.12 (m, 8H, phenyl), 4.10~3.82 (m, 4H, the 2-CH that link to each other with phenyl
2O-), 3.60~3.30 (s, 34H, 2-OCH<and 16-CH
2O-), 1.08 (m, 6H, 2-CH
3), (KBr salt sheet is filmed cm to FTIR
-1): 3375 (s, v
O-H), 2880 (m, v
C-H), 1670 (s, v
C=O);
(d) under protection of nitrogen gas; with 3 of 3g; 3 '-two [3-(2-hydroxyl-3-tri ethylene glycol ethyl ether base-propane-1-oxygen base)]-benzils; the phenyl aldehyde of 3g; the mixture of the ammonium acetate of 15g and the Glacial acetic acid of 60g refluxed 24 hours down at 120 ℃; after the cooling reactant is poured in the 3wt% aqueous solution of sodium bisulfite of 300g; filter and promptly get 2.9g2-phenyl-4; 5-two [3-(2-hydroxyl-3-tri ethylene glycol ethyl ether base-propane-1-oxygen base)-phenyl]-imidazoles white powder; yield is 85%; fusing point is 52~56 ℃
1H NMR (DMSO-d6,400MHz, ppm): 12.76 (s, 1H, N-H), 7.56~7.10 (m, 13H, phenyl), 4.10~3.82 (m, 4H, the 2-CH that link to each other with phenyl
2O-), 3.60~3.30 (s, 34H, 2-OC<and 16-CH
2O-), 1.08 (m, 6H, 2-CH
3); FTIR (KBr, cm
-1): 3375 (m, v
O-H), 3250 (m, v
N-H), 2975 (m, v
C-H), 1605 (s, v
C=C)
(e) with the 2-phenyl-4 of 2g, 5-two [3-(2-hydroxyl-3-tri ethylene glycol ethyl ether base-propane-1-oxygen base)-phenyl]-imidazoles is dissolved in the pimelinketone of 20g, slowly be added drop-wise to the tetra-n-butyl ammonium bromide that 4g is housed then, in the flask of the 40wt% aqueous sodium hydroxide solution of the Tripotassium iron hexacyanide of 10g and 20g, refluxed 24 hours down at 60 ℃, the cooling back adds the distilled water of 100g, behind distilled water wash, use anhydrous sodium sulfate drying by the organic phase that the pimelinketone extraction obtains, organic phase after the evaporation concentration poured in the long-pending sherwood oil of decaploid precipitate, filter after first alcohol and water recrystallization promptly gets 2 of 1.1g, 2 '-phenylbenzene-4,4 ', 5,5 '-four [3-(2-hydroxyl-3-tri ethylene glycol ethyl ether base-propane-1-oxygen base)-phenyl]-1,2 '-diimidazole pale yellow crystals, yield is 55%, and fusing point is 66~70 ℃
1H NMR (DMSO-d6,400MHz, ppm): 7.56~7.11 (m, 26H, phenyl), 4.10~3.82 (m, 8H, the 4-CH that link to each other with phenyl
2O-), 3.60~3.30 (s, 68H, 4-OCH<and 32-CH
2O), 1.08 (m, 12H, 4-CH
3), FTIR (KBr, cm
-1): 3375 (m, v
O-H), 2975 (s, v
Methyl C-H), 2872 (s, v
Methylene radical C-H), 1605 (s, v
C=C), MALDI-TOF-MS:m/e 1592 (M+1).