2-(Ethoxymethylene)propanedinitrile → HCID 57504673, compound

(Ethoxymethylene)malononitrile (CAS no. 123-06-8) (3.18 g, 26.04 mmol) was added portionwise to the stirred solution of (5-fluoro-2-methylphenyl)hydrazine hydrochloride (CAS no. 325-50-8) (4.6 g, 26.04 mmol) and N,N-diisopropylethylamine (5.90 mL, 33.86 mmol) in MeOH (50 mL), under nitrogen at 5° C. The resulting solution was allowed to stir for a further 30 minutes at this temperature. The reaction mixture was then heated to reflux and was stirred for 3 hours. The reaction mixture was allowed to cool to ambient temperature. The reaction mixture was evaporated to dryness, redissolved in EtOAc (200 mL), washed with water (50 mL), and saturated brine (50 mL). The organic layer was dried (MgSO4), filtered and evaporated to afford crude product. This was purified by flash silica chromatography, elution gradient 0 to 50% EtOAc in isohexane to afford the product (1.076 g, 19.11%). 1H NMR (400 MHz, DMSO) δ 2.00 (3H, s), 6.56 (2H, s), 7.20 (1H, dd), 7.29 (1H, td), 7.43 (1H, t), 7.75 (1H, s); m/z (ES+) (M+H)+=217; HPLC tR=1.61 min.

1. customat 5° C
2. temperatureThe reaction mixture was then heated
3. temperatureto reflux
4. stirringwas stirred for 3 hours
5. customThe reaction mixture was evaporated to dryness
6. dissolutionredissolved in EtOAc (200 mL)
7. washwashed with water (50 mL), and saturated brine (50 mL)
8. dry with materialThe organic layer was dried (MgSO4)
9. filtrationfiltered
10. customevaporated
11. customto afford crude product
12. customThis was purified by flash silica chromatography, elution gradient 0 to 50% EtOAc in isohexane

ORD record

ord-a37c234b992e4b6faf5089a38d80470a

Source dataset

uspto-grants-2012_03

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08143263B2