4-Iodo-2-nitrobenzaldehyde → racemic (RS)-1-(4-Iodo-2-nitrophenyl)ethanol

Temperature

0 °C

Titanium(IV) isopropoxide (1.2 mL, 4.04 mmol) was dissolved in anhydrous dichloromethane (8 mL) under a nitrogen atmosphere. The solution was cooled to 0° C. and dimethylzinc (2 M in toluene, 8.67 mL, 17.34 mmol) was added dropwise. The mixture was stirred at 0° C. for 45 minutes followed by addition of 4-iodo-2-nitrobenzaldehyde (800 mg, 2.89 mmol). The mixture was stirred at 0° C. for 36 hours, then quenched by 1M HCl (CAUTION: vigorous gas evolution!) and extracted with ethyl either (50 mL) three times. The combined organic phase was washed with water (50 mL), saturated NaHCO3 solution (50 mL) and brine (50 mL), dried over Na2SO4, concentrated in vacuo, and purified by column chromatography to yield racemic (RS)-1-(4-Iodo-2-nitrophenyl)ethanol (408 mg, 48%). 1H NMR (400 MHz, CDCl3): δ 8.21 (dd, 1H, J=1.8 and 5.3 Hz, Ph-H), 7.96 (m, 1H, Ph-H), 7.58 (d, 1H, J=8.3 Hz, Ph-H), 5.38 (q, 1H, J=6.1 Hz, Ph-CH), 2.34 (br s, 1H, OH), 1.54 (d, 3H, J=6.1 Hz, CH3); 13C NMR (100 MHz, CDCl3): δ 147.98 (C), 142.49 (CH), 140.68 (C), 132.77 (CH), 131.31 (CH), 91.60 (C), 65.40 (CH), 24.28 (CH3).

1. stirringThe mixture was stirred at 0° C. for 36 hours
2. customquenched by 1M HCl (CAUTION: vigorous gas evolution!)
3. extractionextracted with ethyl either (50 mL) three times
4. washThe combined organic phase was washed with water (50 mL), saturated NaHCO3 solution (50 mL) and brine (50 mL)
5. dry with materialdried over Na2SO4
6. concentrationconcentrated in vacuo
7. custompurified by column chromatography

ORD record

ord-7cd7197e221b416983d41ef60be29a0a

Source dataset

uspto-grants-2014_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08877905B2