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Rk. mit Paraformaldehyd -> 4-(β-Chlormethoxy-ethoxy)-2-hydroxy-benzophenon;
Yield
Reaction Conditions
Operation in experiment
BrCH2CH2OH, entspr. Benzophenon;
/BRN= 311566/, ClCH2CH2OH, in wss. A., Na2CO3;
7
2-(4-benzoyl-3-hydroxyphenoxy)ethyl chloroformate[ No CAS ]
[ 16909-78-7 ]
2-(4-Benzoyl-2-hydroxyphenoxy)ethyl Chloroformate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In dichloromethane
19 Endcapping of Jeffamine M-600 with 2-(4-Benzoyl-2-hydroxyphenoxy)ethyl Chloroformate (Compound I-19)
EXAMPLE 19 Endcapping of Jeffamine M-600 with 2-(4-Benzoyl-2-hydroxyphenoxy)ethyl Chloroformate (Compound I-19) A solution of 11.8 g (35.0 mmoles) of 95.4% 2-(4-benzoyl-3-hydroxyphenoxy)ethyl chloroformate in 50 mL of dry methylene chloride was added at room temperature to 20.0 g (35.0 mmoles) of Jeffamine M-600 (a monoamino oligomeric polyether with a molecular weight of about 600 based on 2.80 weight % amino groups, produced by Texaco, Inc.) in 75 mL of dry methylene chloride. The resulting solution was stirred for 12 hours at room temperature. The reaction mixture was then washed four times with 5% aqueous sodium hydroxide solution and once with saturated sodium hydrogen carbonate solution. The solution was dried over anhydrous magnesium sulfate and after separation of the spent desiccant by filtration the methylene chloride was removed in vacuo. 26.1 g (theory, 29.9 g) of a light amber oil resulted. Analysis by high performance LC indicated that there was less than 0.1% of residual 2-hydroxy-4-(2-hydroxyethoxy)benzophenone in the product. The UV spectrum of the product was similar to that of 2-hydroxy-4-(2-hydroxyethoxy)benzophenone, which showed that the desired product was formed. Analysis by ultraviolet (UV) spectroscopy showed that the product contained about 29.8 weight % (theory, 30.1 weight %) of attached 2-(4-benzoyl-3-hydroxyphenoxy)ethoxycarbonyloxy) UV absorbing groups. Based on the method of preparation and analyses, the product formed in this reaction, I-19, was a mono(2-(4-benzoyl-3-hydroxyphenoxy)ethoxycarbonylamino) endcapped Jeffamine M-600 oligomer.
5 EXAMPLE 5
EXAMPLE 5 A mixture of 21.4 parts (0.1 mole) of 2,4-dihydroxybenzophenone, 9.7 parts (0.11 mole) of ethylene carbonate and 1.9 parts (0.005 mole) hexadecyltrimethylammonium bromide was heated for 11 hours at 150° C. to 160° C. The reaction was cooled to about 100° C. and water was added, the pH was adjusted to about 7.5-8 using a small amount of dilute sodium hydroxide. The reaction mixture was stirred an additional 3 hours and the precipitate was suctioned off. After washing and drying 22 parts of 2-hydroxy-4-(2'-hydroxyethoxy)benzophenone (85 percent of the theoretical) was obtained.
4 Embodiment 4
Embodiment 4 2-Hydroxy 4-(2-maltoxyethoxy) benzophenone 1 g of 2,4-dihydroxy benzophenone was added to and dissolved in 7 g of ethylbromohydrin, 37 mg of sodium hydroxide and 0.25 g of purified water. The solution was heated to 100° C. and stirred and then cooled to 90° C. Furthermore, 224 mg of sodium hydroxide was added to the mixture. The mixture was heated and stirred for 2 hours, and then cooled. The resultant was extracted with chloroform, washed with water, and condensed by removing the water. The product was purified using the silica gel chromatography (Toluene: Methylethyl ketone), and 1.1 g of 2-hydroxy 4-(2-hydroxyethoxy) benzophenone was obtained.
With triethylamine In tetrahydrofuran at -25℃; for 3.25h;
2-chloro-2-oxo-l,3,2-dioxphospholane (CAS: 6609-64-9, 1.02 g, 7.1 mmol) was dissolved in dry tetrahydrofuran (20 mL) and cooled to -25°C. Triethylamine (0.724 g, 7.1 mmol) was then added to the cold solution. Hydrolysed BP15 or BP15-dE (1.85 g, 7.1 mmol) was dissolved in dry tetrahydrofuran (15 mL) and added dropwise to the phospholane solution over the course of 15 minutes. A further 5 mL of tetrahydrofuran was used to rinse the remainder of the BP15-dE into the flask. The mixture was stirred at -25°C for 3 hours after which the triethylammonium salt was filtered off and the tetrahydrofuran removed under vacuum to give a pale yellow oil. The crude product (2.65 g) was used without purification in the next step.
2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate[ No CAS ]
[ 16909-78-7 ]
Yield
Reaction Conditions
Operation in experiment
With sodium hydroxide for 1h;
10 g of 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate or BP15 (CAS: 16432-81-8, 10 g, 38.7 mmol) was mixed with 200 mL of 2M sodium hydroxide (NaOH) solution. After one hour stirring, the pH was lowered to 1 with concentrated hydrochloric acid (HC1). A white product precipitated and was filtered off. The product was solubilised in dichloromethane and washed with water by liquid extraction for purification. After solvent removal, the hydrolysed BP15 or BP15-dE was dried for two days under vacuum.
2-methyl-2-propenoic acid-2-[[[2-(4-benzoyl-3-hydroxy-phenoxy)ethoxy]carbonyl]amino]ethyl ester[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
Stage #1: 2-Isocyanatoethyl methacrylate; 2-hydroxy-4-(2'-hydroxyethoxy)benzophenone With dmap; 4-methoxy-phenol at 0 - 20℃; for 1.5h;
Stage #2: With 1,8-diazabicyclo[5.4.0]undec-7-ene at 20 - 30℃; for 6h;
Stage #3: In ethanol; isopropyl alcohol at 60℃; for 0.5h;
1; 1.1-1.2; 2; 2.1-2.2; 3.1-3.2 The catalysts of this embodiment are DMAP and DBU:
(1) in 20L reactor, add 6000mL methylene chloride,12.2g DMAP, then 2.6kg 2(2-hydroxy-4-(2-hydroxyethoxy)phenyl)(phenyl)methanone and 1.8g polymerization inhibitor MEHQ were added. After stirring to dissolve, the temperature was lowered to 0°C. 1.75kg of isocyanoethyl methacrylate was added to the overhead tank, and then 1000mL of dichloromethane was added to dilute. The diluted isocyanoethyl methacrylate was slowly added to the reaction solution, the dropwise addition time was 1 h, and the temperature during the dropwise addition was 20°C. After the dropwise addition was completed, the reaction was kept at 20°C for 0.5h. At 20° C., 75 g of DBU was added dropwise to the reaction solution for 1 h. After the dropwise addition, the reaction was kept at 30 °C for 5 h. After TLC (PE:EA=1:1, UV254nm color development) detected the reaction of 2(2-hydroxy-4-(2-hydroxyethoxy)phenyl)(phenyl)methanone, the reaction was stopped. 5N hydrochloric acid solution was slowly added to the reaction solution to adjust the pH to 5-6. The lower organic phase was dried over anhydrous sodium sulfate, filtered and concentrated to obtain 4.7 kg of crude product.(2) Add 1.88kg isopropanol and 5.64kg ethanol to the crude product (the mass ratio of the solvent to the crude product is 1.6:1), heat to 60° C., and stir the solid for 30 min. Filter (the upper layer of the filter device is covered with silica gel with a thickness of 3 cm, the silica gel is 100-200 mesh), the temperature is lowered to 0° C. for crystallization for 3 h, centrifuged and dried.
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