Ethylparaben → HCID 11058114, compound

Sodium hydride (1.55 g, 61 mmol) was suspended in DMF (150 mL) under an atmosphere of nitrogen. Ethyl-4-hydroxybenzoate (11) (5.06 g, 30 mmol) was added as a solution in DMF (30 mL) via syringe which was then washed with DMF (2×5 mL). The reaction mixture was then stirred at room temperature under an atmosphere of nitrogen for 2 hours. After this time, 1,10-dibromodecane (30.84 g, 103 mmol) was added as a solution in DMF (50 mL) via syringe which was then washed with DMF (2×5 mL). The reaction mixture was then stirred at room temperature under nitrogen for 19 hours. The reaction was quenched with water (200 mL) and the organic fragments extracted with diethyl ether (4×150 mL), dried over MgSO4, and excess solvent removed in vacuo to form a colorless oil. This was purified by flash column chromatography using CH2Cl2/hexane (1:1) to CH2Cl2/hexane (3:1) as eluting solvents to form a white crystalline solid. This was recrystallized from ethanol to form 4-(10-bromo-decyloxy)-benzoic acid ethyl ester (7.38 g, 19.1 mmol, 63%). Rf 0.65 (CH2Cl2), mp 41-42° C. FTIR, νmax/cm−1 1 3023, 2927, 2855, 1708, 1604, 1509, 1468, 1390, 1367, 1312, 1252, 1155, 1018, 851, 772. 1H NMR (CDCl3, 250 MHz), δ/ppm 7.96 and 6.87 (both 2 H, m, Ar—H); 4.32 (2 H, q, 3J=7.1 Hz, −CH2CH3); 3.97 (2 H, t, 3J=6.5 Hz, —OCH2—); 3.38 (2 H, t, 3J=6.9 Hz, —CH2Br); 1.80 (4 H, m, —OCH2CH2— and —CH2CH2Br); 1.42-1.27 (15 H, m, alkyl C—H). 13C{1H} NMR (CDCl3, 63 MHz), δ/ppm 166.2 (C=O); 152.6 and 122.4 (quat. Ar C); 131.3 and 113.8 (Ar C—H); 67.9 and 60.4 (—OCH2—); 33.9, 32.6, 29.2, 29.1, 29.0, 28.9, 28.5, 28.0, 25.8 (CH2); 14.2 (—CH3) λmax/nm (ε/dm3mol−1cm−1) 257 (24641). HRMS (FAB), M+/z C19H30BrO3 (MH+) requires 385.1378, found 385.1374.

1. washwas then washed with DMF (2×5 mL)
2. washwas then washed with DMF (2×5 mL)
3. stirringThe reaction mixture was then stirred at room temperature under nitrogen for 19 hours
4. customThe reaction was quenched with water (200 mL)
5. extractionthe organic fragments extracted with diethyl ether (4×150 mL)
6. dry with materialdried over MgSO4, and excess solvent
7. customremoved in vacuo
8. customto form a colorless oil
9. customThis was purified by flash column chromatography
10. washas eluting solvents
11. customto form a white crystalline solid
12. customThis was recrystallized from ethanol

ORD record

ord-2ffb856ebb30419e8d13bd5f6688747a

Source dataset

uspto-grants-2003_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06566520B2