| 85.9% |
Stage #1: phenylphosphonous acid dimethyl ester; mesitylene-2-carboxylic acid chloride at 23℃; for 18h; Inert atmosphere;
Stage #2: With lithium bromide In butanone at 50℃; Inert atmosphere; |
13 Lithium Phenyl-2,4,6-Trimethylbenzoylphosphinate (LAP) Photoinitiator Synthesis
Example 13 Lithium Phenyl-2,4,6-Trimethylbenzoylphosphinate (LAP) Photoinitiator Synthesis LAP was synthesized as previously reported. See, Majima, T.; Schnabel, W.; Weber, W., "Phenyl-2,4,6-trimethylbenzoylphosphinates as water-soluble photoinitiators. Generation and reactivity of O=P(C6H5)(O-) radical anions." Die Makromolekulare Chemie 1991, 192 (10), 2307-2315, the disclosure of which is incorporated herein by reference in its entirety. Briefly, 2.80 mL of dimethyl phenylphosphonite (17.6 mmol, 1.00 eq) was added to an oven dried flask under Ar at 23° C. While stirring, 2.94 mL of 2,4,6-trimethylbenzoyl chloride (17.6 mmol, 1.00 eq) was added dropwise and allowed to react for 18 h. Then, a four-fold excess of LiBr (6.1 g) in 100 mL of 2-butanone was added to the reaction mixture and heated to 50° C. for 10-15 min with stirring until a white precipitate formed. The solution was cooled to room temperature and set for 2 h, then suction filtered and rinsed generously with 2-butanone to remove excess LiBr. The solid white precipitate (4.45 g, 85.9% yield) was dried under vacuum and analyzed by 1H-NMR and UV-visible spectroscopy. (1H-NMR (300 MHz, 303K, D2O): δ=2.01 (s, 6H), 2.23 (s, 3H), 6.88 (s, 2H), 7.41-7.51 (m, 2H), 7.51-7.61 (m, 1H), 7.70 (m, 2H) ppm. UV-vis (H2O), λabs=372 nm, ε=179+-3 M-1cm-1 (lit. value=218 M-1cm-1)). The molar absorptivity (ε) was determined and compared to the literature (observed=179+-3 M-1cm-1, lit. value=218 M-1cm-1). See, Fairbanks, B. D.; Schwartz, M. P.; Bowman, C. N.; Anseth, K. S., "Photoinitiated polymerization of PEG-diacrylate with lithium phenyl-2,4,6-trimethylbenzoylphosphinate: polymerization rate and cytocompatibility." Biomaterials 2009, 30 (35), 6702-6707, the disclosure of which is incorporated herein by reference in its entirety. |
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Stage #1: phenylphosphonous acid dimethyl ester; mesitylene-2-carboxylic acid chloride for 18h;
Stage #2: With lithium bromide In butanone at 50℃; |
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Stage #1: phenylphosphonous acid dimethyl ester; mesitylene-2-carboxylic acid chloride at 20℃; for 24h; Inert atmosphere;
Stage #2: With lithium bromide In butanone at 20 - 50℃; Inert atmosphere; |
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Stage #1: phenylphosphonous acid dimethyl ester; mesitylene-2-carboxylic acid chloride at 20℃; for 18h; Inert atmosphere;
Stage #2: With lithium bromide In butanone at 50℃; for 0.166667h; |
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Stage #1: phenylphosphonous acid dimethyl ester; mesitylene-2-carboxylic acid chloride at 50℃; for 18h; Inert atmosphere;
Stage #2: With lithium bromide In butanone at 50℃; for 10h; Inert atmosphere; |
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Stage #1: phenylphosphonous acid dimethyl ester; mesitylene-2-carboxylic acid chloride at 20℃; for 18h; Inert atmosphere;
Stage #2: With lithium bromide In butanone at 20 - 50℃; for 4.16667h; |
2 Synthesis of a LithiumPhenyl-2,4,6-trimethylbenzoylphosphinate (LAP)Photoinitiator
Synthesis of a LithiumPhenyl-2,4,6-trimethylbenzoylphosphinate (LAP)Photoinitiator10299] Lithium phenyl-2,4,6-trimethylbenzoylphosphi- nate (LAP) photoinitiator was synthesized as described previously by Fairbanks et al (Biomaterials 2009; 30:6702- 6707). Briefly, 2,4,6-trimethylbenzoyl chloride (ChemImpex Int’l Inc.) was added dropwise to an equimolar amount of dimethyl phenylphosphonite (Alfa Aesar) at RT under nitrogen atmosphere. After mixing for 18 h, a four fold excess of lithium bromide (Strem Chemicals) dissolved in 2-bu- tanone (Acros Organics) was added to the mixture and reaction was continued for 10 mm at 50° C. Afier heating, the mixture was kept at RT for 4 h, and the resulting precipitate was filtered and washed with 2-butanone and diethyl ether and dried under vacuum. |
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Stage #1: phenylphosphonous acid dimethyl ester; mesitylene-2-carboxylic acid chloride at 20℃; for 24h;
Stage #2: With lithium bromide In butanone at 50℃; for 0.166667h; |
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Stage #1: phenylphosphonous acid dimethyl ester; mesitylene-2-carboxylic acid chloride at 20℃; Inert atmosphere;
Stage #2: With lithium bromide at 50℃; for 0.166667h; Inert atmosphere; |
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| 6 g |
Stage #1: phenylphosphonous acid dimethyl ester; mesitylene-2-carboxylic acid chloride at 20℃; for 18h; Inert atmosphere;
Stage #2: With lithium bromide In butanone at 50℃; for 0.166667h; |
155 Synthesis of a photoinitiator agent of -LAP:
Synthesis of LAP: Dimethoxyphenylphosphine (3.0 g, 0.018 mol) was placed in a 250 mL three-necked flask and protected with argon. 2,4,6-Trimethylbenzoyl chloride (3.2 g, 0.018 mol) was added, and the reaction was stirred at room temperature for 18 h, then lithium bromide (6.1 g, 0.072 mol) was dissolved in 100 mL of 2-butanone. After adding to the above reaction liquid, the mixture was heated to 50 ° C for 10 minutes, and a precipitate was formed. After cooling to room temperature for 4 hours, it was filtered, and the obtained crude product was washed with 2-butanone several times. After drying, a white solid LAP (6.0 g) was obtained. |
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