Guanidine Hydrochloride → HCID 58513944, compound

Norcamphor (6.11 g, 55.5 mMol) was heated with t-butoxy bis(dimethylamino)methane (Bredereck's reagent, 9.7 g, 55.5 mmol) at 100° C. overnight. The solvent was removed under vacuum and the crude residue was taken up in anhydrous ethanol (120 mL). Guanidine hydrochloride (10.6 g, 110 mmol, 2 eq.) and sodium metal (2.5 g, 110 mmol) were added. After the sodium dissolved, the mixture was heated to reflux for 48 h. After cooling to ambient temperature, sodium metal (0.47 g) and guanidine hydrochloride (2.0 g) were added and heating was resumed for another 24 h. The reaction mixture was concentrated under vacuum and then partitioned between chloroform and water. The aqueous layer was extracted once with chloroform. The combined organic layers were washed with saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate and concentrated to give 2-amino-5,8-methano-5,6,7,8-tetrahydroquinazoline as a pale yellow solid; 1H NMR (CDCl3, 300 MHz) 7.89 (s, 1H), 5.07 (br s, 2H), 3.31 (s, 1H), 3.16 (s, 1H), 1.93 (m, 2H), 1.74 (d, 1H), 1.53 (d, 1H), 1.25 (m, 2H) ppm; 13C NMR (CDCl3, 75 MHz) 179.44, 147.43 (2C), 128.79, 47.51, 45.41, 39.85, 27.81, 25.42; MS(ES) 162 (M+H). The aniline, 2-amino-5,8-methano-5,6,7,8-tetrahydroquinazoline, can be used to make the corresponding hydrazine as outlined below, or alternatively, can be used as an aniline (B) as outlined in Reaction Scheme 1 above.

1. customThe solvent was removed under vacuum
2. temperaturethe mixture was heated
3. temperatureto reflux for 48 h
4. temperatureheating
5. concentrationThe reaction mixture was concentrated under vacuum
6. custompartitioned between chloroform and water
7. extractionThe aqueous layer was extracted once with chloroform
8. washThe combined organic layers were washed with saturated aqueous sodium chloride solution
9. dry with materialdried over anhydrous sodium sulfate
10. concentrationconcentrated

ORD record

ord-ea12c93175c54b7fa3d0d24ba089ee3c

Source dataset

uspto-grants-2011_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08012965B2