2-hydroxy-2-methyl-1-phenylpropan-1-one

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under nitrogen atmosphere 100 grams of Darocur 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one) was placed in 2 L of dry chloroform. After the mixture was cooled to 0° C., 480 grams of anhydrous AlCl3 and 55 grams of paraformaldehyde powder were successively added and the resultant mixture was vigorously stirred at 60° C. overnight for 14 hrs (note that HCl gas released from the reaction was neutralized by 2N NaOH solution). An additional portion of 55 grams of paraformaldehyde was added at this point and the reaction was stirred at this temperature for another 12 hrs. The mixture was cooled to room temperature, and under vigorous stirring poured into 3 L of water. The organic layer thus separated was collected, and the aqueous layer was extracted with 1 L of dichloromethane for three times. The combined chloroform and dichloromethane layer was next dried over anhydrous Na2SO4, filtered, and concentrated. The residue was loaded onto silica gel column and gradient eluted by mixtures of hexane/ethyl acetate (V/V=15/1 to 12/1) to give the intermediate 1-(3-(chloromethyl)phenyl)-2-hydroxy-2-methylpropan-1-one as a light-yellow oil (77.4% yield), and four other by-products A-D (22.6% combined yield). Characterization data for compound A (11.7% yield): 1H NMR (CDCl3, ppm): 8.01 (s, 2H), 7.63 (s, 1H), 4.63 (s, 4H), 3.78 (s, 1H), 1.62 (s, 6H); 13C NMR (CDCl3, ppm): 203.7, 138.5, 135.0, 132.7, 129.7, 76.7, 45.2, 28.3; Compound B (2.6% yield): 1H NMR (CDCl3, ppm): 7.93 (s, 2H), 7.82 (s, 2H), 7.43 (s, 2H), 4.60 (s, 4H), 4.12 (s, 2H), 3.82 (s, 2H), 1.59 (s, 12H); Compound C (3.1% yield): 1H NMR (CDCl3, ppm): 7.89 (dd, 2H), 7.86 (s, 2H), 7.42-7.40 (m, 4H), 4.10 (s, 2H), 4.05 (s, 2H), 1.60 (s, 12H); 13C NMR (CDCl3, ppm): 204.7, 140.8, 134.2, 133.4, 130.1, 128.7, 127.8, 76.5, 41.5, 28.4; Compound D (4.9% yield): 1H NMR (CDCl3, ppm): 10.06 (s, 1H), 8.54 (s, 1H), 8.31 (d, 1H, J=7.5 Hz), 8.06 (d, 1H, J=7.6 Hz), 7.62 (dd, 1H, J=7.5 Hz, J=7.6 Hz), 3.89 (s, 1H), 1.61 (s, 6H); 13C NMR (CDCl3, ppm): 203.4, 191.9, 136.0, 135.5, 135.3, 132.6, 131.5, 128.9, 77.0, 27.9. The mixture was cooled to room temperature under vigorous stirring The organic layer thus separated was collected the aqueous layer was extracted with 1 L of dichloromethane for three times The combined chloroform and dichloromethane layer was next dried over anhydrous Na2SO4 filtered concentrated gradient eluted by mixtures of hexane/ethyl acetate (V/V=15/1 to 12/1) to give

反応条件: temp:4.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: under nitrogen atmosphere 5 grams of Darocur 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one) was mixed with 24 grams of anhydrous AlCl3 in 100 mL of dry chloroform. Upon cooling to 4° C. 4.5 grams of paraformaldehyde powder was slowly added and the resultant mixture was stirred at room temperature for 12 hrs (note that HCl gas released from the reaction was neutralized by 2N NaOH solution). The mixture was poured into water, and the precipitate generated was dissolved by adding 2N HCl solution. The organic layer thus separated was collected, and the aqueous layer was extracted with ethyl acetate for three times. The combined chloroform and ethyl acetate layer was next dried over anhydrous Na2SO4, filtered, and concentrated. The residue was loaded onto silica gel column and eluted by mixtures of hexane/ethyl acetate (V/V=15/1) to give the intermediate 1-(3-(chloromethyl)phenyl)-2-hydroxy-2-methylpropan-1-one as a light-yellow oil (33% yield). the precipitate generated was dissolved The organic layer thus separated was collected the aqueous layer was extracted with ethyl acetate for three times The combined chloroform and ethyl acetate layer was next dried over anhydrous Na2SO4 filtered concentrated eluted by mixtures of hexane/ethyl acetate (V/V=15/1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-Hydroxy-isobutyrophenone was prepared from phenol following the procedure described in Canadian Journal of Chemistry, 31, 1956, 851. To a solution of 2-hydroxy-isobutyrophenone (2g, 12.2 mmol) in trifluroacetic acid (14 g, 122 mmol) was slowly added triethylsilane (26.8 mmol). The solution was stirred at room temperature for 6 hours. Saturated sodium bicarbonate solution was added to the reaction mixture, followed by ether. The layers were separated, and the aqueous layer was extracted with ether. The organic layers were combined, dried over magnesium sulfate, and concentrated. The crude material was distilled under vacuum (about 9.3×10−4 MPa, 75° C.). The distillate was washed with potassium hydroxide solution, followed by addition of hydrogen chloride solution, and extraction with ether. The ether layers were combined, dried over magnesium sulfate, and concentrated to give 1.0 g (55%) of 2-isobutylphenol. 1H NMR (300 Mhz, δ, CDCl3): 7.0 (m, 2H), 6.8 (t, 1H), 6.7 (d, 1H), 4.6 (br. s, 1H), 2.4 (d, 2H), 1.9 (s, 1H), 0.9 (d, 6H). The layers were separated the aqueous layer was extracted with ether dried over magnesium sulfate concentrated The crude material was distilled under vacuum (about 9.3×10−4 MPa, 75° C.) The distillate was washed with potassium hydroxide solution followed by addition of hydrogen chloride solution, and extraction with ether dried over magnesium sulfate concentrated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,-4-diethylthioxanthone 2-ethylanthraquinone; 2-methylanthraquinone; 1,8-dihydroxyanthraquinone; dibenzoylperoxide; 2,2-dimethoxy-2-phenylacetophenone; benzoin; 2-hydroxy-2-methylpropiophenone; benzaldehyde; 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-methylpropyl)-ketone; benzoylacetone;

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Examples of commercially available radical photopolymerization initiator include IRGACURE 651 (2,2-dimethoxy-1,2-diphenyl ethane-1-on), IRGACURE 184 (1-hydroxycyclohexyl-phenyl-ketone), DAROCUR 1173 (2-hydroxy-2-methyl-1-phenyl-propane-1-on), IRGACURE 2959 (1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-on), IRGACURE 127 (2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propnyl)-benzyl]phenyl}-2-methyl-propane-1-on, IRGACURE 907 (2-methyl-1-(4-methyl thiophenyl)-2-morpholinopropane-1-on), IRGACURE 369 (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1), IRGACURE 379 (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), DAROCUR TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), IRGACURE 819 (bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide), IRGACURE 784 (bis(eta-5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl)titanium), IRGACURE OXE 01 (1.2-octanedione, 1-[4-(phenylthio)-, 2-(o-benzoyloxime)]), IRGACURE OXE 02 (ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(o-acetyloxime)), and IRGACURE 754 (mixture of oxyphenyl acetic acid, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester and oxyphenyl acetic acid, 2-(2-hydroxyethoxy)ethyl ester)(all produced by BASF); Speedcure TPO (produced by Lambson), KAYACURE DETX-S (2,4-diethylthioxantone) (produced by Nippon Kayaku Co., Ltd.); Lucirin TPO, LR8893, LR8970 (produced by BASF); Ubecryl P36 (produced by UCB), and the like. all produced by BASF)

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-methyl-1-[4-(methyl thio)-phenyl]-2-morpholinopropanone-1; 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one; 1-(4-dodecyl-phenyl)-2-hydroxy-2-methylpropan-1-one; 4-(2-hydroxyethoxy)phenyl-2(2-hydroxy-2-propyl)-ketone; diethoxyphenyl acetophenone; 2,4,6 trimethylbenzoyl diphenylphosphone, a mixture of (2,6-dimethoxy benzoyl)-2,4,4 trimethylpentylphosphineoxide and 2-hydroxy-2-methyl-1-phenyl-propane-1-one, and mixtures thereof.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-methyl-1-[4-(methyl thio)-phenyl]-2-morpholinopropanone-1; 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one; 1-(4-dodecyl-phenyl)-2-hydroxy-2-methylpropan-1-one; 4-(2-hydroxyethoxy)phenyl-2(2-hydroxy-2-propyl)-ketone; diethoxyphenyl acetophenone; 2,4,6 trimethylbenzoyl diphenylphosphone, a mixture of (2,6-dimethoxy benzoyl)-2,4,4 trimethylpentylphosphineoxide and 2-hydroxy-2-methyl-1-phenyl-propane-1-one, and mixtures thereof.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Other examples are IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379, DAROCUR TPO, IRGACURE 819, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, and IRGACURE 754 (all are manufactured by Ciba Specialty Chemicals).

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Other examples are IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379, DAROCUR TPO, IRGACURE 819, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, and IRGACURE 754 (all are manufactured by Ciba Specialty Chemicals).

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Other examples are Irgacure 2959, Irgacure 127, Irgacure 907, Irgacure 369, Irgacure 379, Darocur TPO, Irgacure 819, Irgacure 784, Irgacure OXE01, Irgacure OXE02, and Irgacure 754 (all are manufactured by Ciba Specialty Chemicals).