Chlorosuccinimide → Alpha-chlorobenzaldoxime

To a colorless, homogeneous solution of (E)-benzaldehyde oxime (24.4 g, 201 mmol) in N,N-dimethylformamide (60 mL) at room temperature was added N-chlorosuccinimide (26.9 g, 201 mmol) portion-wise over 30 min. During each addition, the reaction mixture turned yellow and then gradually returned to near colorlessness. Additionally, an exotherm was noted with each portion added. (It was extremely important to make sure that the reaction was initiated after the addition of the first ˜⅕ of the N-chlorosuccinimide.). After the addition was complete, the homogeneous reaction mixture was stirred overnight at room temperature. The reaction mixture was diluted with 250 mL of water and extracted with ether (3×100 mL). The organic layers were combined, washed with water (2×100 mL), 10% aqueous solution of lithium chloride (2×100 mL), and brine (100 mL). The four aqueous layers were back extracted with ether (100 mL), and the combined organic layers (400 mL) were dried over anhydrous sodium sulfate. Concentration under reduced pressure afforded (Z)—N-hydroxybenzimidoyl chloride (30.84 g, 198 mmol, 98% yield) as a fluffy, pale yellow solid. The product had an HPLC ret. time=1.57 min. (condition A); LC/MS M+1=155.8; 1H NMR (500 MHz, DMSO-d6) δ ppm 7.30-7.64 (m, 3H), 7.73-7.87 (m, 2H), and 12.42 (s, 1H).

1. additionDuring each addition
2. additionadded
3. additionAfter the addition
4. extractionextracted with ether (3×100 mL)
5. washwashed with water (2×100 mL), 10% aqueous solution of lithium chloride (2×100 mL), and brine (100 mL)
6. extractionThe four aqueous layers were back extracted with ether (100 mL)
7. dry with materialthe combined organic layers (400 mL) were dried over anhydrous sodium sulfate
8. concentrationConcentration under reduced pressure

ORD record

ord-5bcc8b52958e4aa1bae5e737099a15ec

Source dataset

uspto-grants-2015_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09216972B2