Tyramine → HCID 66598932, compound

Temperature

0 °C

10.0 Gram (43.4 mmol) of 2-methacryloyloxyethyl succinate, 10.0 g (52.1 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and 7.04 g (52.1 mmol) of 1-hydroxy-1H-benzotriazole were dissolved in 120 mL of N,N-dimethylformamide, and the resulting solution was cooled to 0° C. in a nitrogen stream and stirred for 0.5 hours. Subsequently, 5.95 g (43.4 mmol) of 4-(2-aminoethyl)phenol was added thereto, and the mixture was stirred at room temperature for 1 hour and further stirred at 60° C. for 4 hours. After adding 200 mL of ethyl acetate, the organic layer was washed, in sequence, three times with an aqueous saturated sodium hydrogencarbonate solution and twice with water and dried over sodium sulfate. The solvent was concentrated to obtain 14.0 g of 2-methacryloyloxyethyl 3-(4-hydroxyphenethylcarbamoyl)propanoate as a brown oil. Thereafter, 6.7 g (19.18 mmol) of this oil and 7.28 g (23.02 mmol) of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl difluoride were dissolved in 100 mL of tetrahydrofuran (THF), and the resulting solution was cooled to 0° C. Thereto, 2.91 g of triethylamine was added dropwise over 0.3 hours, and the obtained reaction solution was stirred at 0° C. for 1 hour and further stirred at room temperature for 12 hours. Thereafter, 50 mL of triethylamine and 5.72 g (38.36 mmol) of trifluoromethanesulfonamide were added thereto, and the mixture was stirred at 50° C. for 4 hours. After adding 200 mL of ethyl acetate, the organic layer was washed, in sequence, twice with dilute hydrochloric acid and twice with water and dried over sodium sulfate. The solvent was concentrated, and the residue was purified by column chromatography (SiO2, ethyl acetate) to obtain 14.4 g of a brown oil. This brown oil was dissolved in 50 mL of methanol, and 5.64 g of triphenylsulfonium bromide was added thereto, followed by stirring at room temperature for 3 hours. After adding 200 mL of chloroform, the organic layer was washed with water, the solvent was concentrated, and the residue was purified by column chromatography (SiO2, ethyl acetate/methanol=6/1), as a result, 8.16 g of a brown transparent oily compound was obtained. 1H-NMR (300 MHz, CDCl3) δ 1.93 (s, 3H), 2.45 (t, 2H), 2.65 (t, 2H), 2.82 (t, 2H), 3.44 (q, 2H), 4.32 (bs, 4H), 5.58 (s, 1H), 6.08 (t, 1H), 6.11 (s, 1H), 7.15 (d, 2H), 7.23 (d, 2H), 7.62-7.79 (m, 15H), 19F-NMR (300 MHz, CDCl3) δ −78.7 (s, 3F), −107.8 (m, 2F), −112.4 (t, 2F), −118.0 (m, 2F).

1. stirringthe mixture was stirred at room temperature for 1 hour
2. stirringfurther stirred at 60° C. for 4 hours
3. washthe organic layer was washed, in sequence, three times with an aqueous saturated sodium hydrogencarbonate solution and twice with water
4. dry with materialdried over sodium sulfate
5. concentrationThe solvent was concentrated

ORD record

ord-f2acfd21432e4270a9a57c4d962c3f55

Source dataset

uspto-grants-2015_06

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09051403B2