Nitroxyl → HCID 565757, compound

Temperature

40 °C

Into a solution of 2.85 g (35 mmol) of cyclohexene in 20 mL of tetrahydrofuran at ambient temperature under nitrogen is added dropwise 12.5 mL (12.5 mmol) of a 1M tetrahydrofuran solution of borane. During addition, reaction temperature is kept under 35° C. Reaction mixture, after addition, is then heated to 40° C. for 2 hours. After cooled to ambient temperature, the reaction is added dropwise into a suspension of 2.15 g (12.5 mmol) of 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl, 1.50 g (37.5 mmol) of sodium hydroxide and 3.17 g (18.8 mmol) of silver nitrate in 40 mL of water at ambient temperature under nitrogen. Thin layer chromatography detects no more starting nitroxyl after 2 hours. Reaction mixture is extracted with 2×10 mL of ethyl acetate and dried over sodium sulfate. Filtration removes inorganic and filtrate is concentrated to an off-white oil. Purification of product by dry-column flash chromatography (20:80/ ethyl acetate:heptane eluent) gives 3.14 g of a white crystalline solid in 98.7% yield: 1H NMR (CDCL3)(300.08 MHz)δ 1.15 (s, CH3, 6 H), 1.20 (s, CH3 ,6H), 1.22, 1.46 (m, CH2, 4H), 1.76, 1.81 (m, CH2, 10H)3.60 (m, CH, 1H),3.90 (m, CH, 1H); MS [M+1]256.

1. additionDuring addition, reaction temperature
2. customis kept under 35° C
3. customReaction mixture
4. additionafter addition
5. temperatureAfter cooled to ambient temperature
6. customafter 2 hours
7. customReaction mixture
8. extractionis extracted with 2×10 mL of ethyl acetate
9. dry with materialdried over sodium sulfate
10. filtrationFiltration
11. customremoves inorganic and filtrate
12. concentrationis concentrated to an off-white oil
13. customPurification of product by dry-column flash chromatography (20:80/ ethyl acetate:heptane eluent)

ORD record

ord-7f660958fa344da9b83ab895b39d5fd1

Source dataset

uspto-grants-2008_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07361755B2