Hydrochloric Acid → N,N-dimethyl-p-phenylenediamine

4-nitroaniline (1.83 g; 13.24 mmol) is added portionwise to cooled (T=+4° C.) formic acid (3 mL; 66.2 mmol). Formaldehyde (37 wt. % solution in water; 2.72 mL; 29.13 mmol) is added and the resulting mixture refluxed for 24 h. After cooling at room temperature 6N HCl is added (2.2 mL) and the formed precipitate is filtered off. The filtrate is diluted with 1N NaOH (5 mL) and extracted with CH2Cl2 (3×20 mL); the organic collected extracts are dried over Na2SO4 and evaporated under vacuum to give a solid residue which, after treatment with a mixture of diisopropyl ether/acetone 1:1 and filtration, gives 4-nitro-N,N-dimethylaniline as a yellow powder (1.65 g; 9.93 mmol). Iron powder (2.145 g; 38.3 mmol) and 37% HCl (28 μl) are suspended in 96% ethyl alcohol (35 mL) and the mixture refluxed for 30′; at the end 4-nitro-N,N-dimethylaniline (0.64 g; 3.84 mmol) is added and the mixture left under reflux and stirring for 2 h. The hot mixture is filter over a Celite pad and, after cooling at room temperature, the filtrate is evaporated under vacuum. The oily residue is diluted with CH2Cl2 (25 mL) and washed with 1N NaOH (3×25 mL), dried over Na2SO4 and evaporated under vacuum to give 4-(N,N-dimethylamino)aniline as pale yellow oil (0.44 g; 3.26 mmol).

1. temperaturethe mixture refluxed for 30′
2. waitthe mixture left
3. temperatureunder reflux
4. filtrationThe hot mixture is filter over a Celite pad
5. customthe filtrate is evaporated under vacuum
6. additionThe oily residue is diluted with CH2Cl2 (25 mL)
7. washwashed with 1N NaOH (3×25 mL)
8. dry with materialdried over Na2SO4
9. customevaporated under vacuum

ORDレコード

ord-744dab6dd743425c8f167b9d2a29cc52

出典データセット

uspto-grants-2012_10

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US08288368B2