4-Amino-N,N-dimethylbenzenemethanamine

To a solution of dimethyl-(4-nitro-benzyl)-amine (Ig, 5.55mmol) in acetic acid (10ml) was added activated iron powder (3g) and the reaction mixture was stirred for 5 hr at 80General procedure: A mixture of compounds 5a–e (0.05 mol) in ethanol was heated to 65 °C, FeClGeneral procedure: A mixture of compounds 5 or 7a-c (0.05 mol) in ethanolwas heated to 65 °C, FeCl3·6H2O (2.8 g, 1 mmol) and activatedcarbon (0.18 g, 15 mmol) were added, and 80percent hydrazinehydrate (25 g, 0.5 mol) was added dropwise at such arate to keep the temperature below 70 °C, the reaction washeated at reflux for 5 h and then cooled to room temperatureand concentrated. Water (100 mL) was added, the reactionsolution was extracted three times with CH2Cl2 (60 mL). Theorganic extracts were combined, dried over sodium sulfate, filtered, and concentrated to obtain the compounds 8a-d.A mixture of 3.5 g (19.4 mmol) of compound (b) in ethanol was heated to 65°C. 0.83 g (0.39 mmol) of FeCl36H2O and 0.07 g (5.85 mmol) of activated carbon were added and 9.8 g (194 mmol) of 80percent hydrazine hydrate was added dropwise at a rate maintaining the temperature below 70°C .The reaction was heated at reflux for 5 hours, cooled to room temperature and concentrated. 500 ml of water was added and the reaction solution was extracted three times with DCM.The organic extracts were mixed, dried over sodium sulfate, and concentrated to obtain 3.2 g (75percent) of a colorless cucumber compound (c).To a 500 ml three-mouth bottle by adding 200 ml of THF, cooling to 5 °C the following add 17.3g (0.46mol, 4 . 0eq) of lithium aluminum hydride, then lower the temperature to the -5 ° C the following, the three aluminum chloride 3.0g (0.023mol, 0 . 2eq) THF slowly dropwise to the reaction in the solution, stirring for 10 min, temperature at 5 °C the following starting to drop plus step amide 19.0g (0.114mol, 1 . 0eq) in 100 ml of solution THF. Added after stirring overnight TLC inspection reaction end, cooling to 0 °C the following, starting the dropping water filtration, the filter cake is washed with dichloromethane eluviation, concentrated filtrate, vacuum distillation, to obtain colorless oily liquid 12.0g product. Yield: 71.0percent, GC: 99.9percentGeneral procedure: 4-(N, N-dimethylamino)aniline 4-nitroaniline (1.83 g; 13.24 mmol) is added portionwise to cooled (T=+4C) 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 24h. 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 (3x20 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 mul) 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 (3x25 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). 1H-NMR (CDCl3): delta 7.10 (d, 2H, J=8Hz); 6.60 (d, 2H, J=8Hz); 3.55 (bs, 2H, NH2); 2.25 (s, 6H).General procedure: The requisite halogen (75 mg, 0.272 mmol, 1.0 eq.), Cs2C03 (266 mg, 0.866 mmol, 3.0 eq.), the requisite amine (53 mg, 0.354 mmol, 1.3 eq.), XPhos (13 mg, 0.027 mmol, 10 mol%) and Pd(OAc)2 (3 mg, 0.014 mmol, 5 mol%) were added sequentially to a microwave vial equipped with a magnetic stirrer bar. The reaction vessel was fitted with a rubber septum and purged with N2 for 5 min, before addition of a degassed solution of 1 , 4-dioxane (3 ml_) via syringe. The vial was then sealed and the reaction heated to 100 C for 24 h. The mixture was cooled down, diluted with EtOAc (30 ml_), and washed with a 50/50 solution of water and brine (2 x 30 ml_). The organic phase was dried (Na2S04) and concentrated in vacuo. Purification by column chromatography on silica gel (solvents as stated) afforded the desired product.General procedure: To the mixture of compounds 4a, b (0.01 mol), dichloromethane (DCM) (20 mL) and pyridine (0.8 mL, 0.02 mol) was added at room temperature, then the mixture was cooled to 0C in an ice-salt bath, phenyl chloroformate was added drop wise at such a rate to keep the temperature below 10C. The reaction mixture was stirred at room temperature for 4-6 h and filtered. The white to light yellow solid was collected and washed with DCM to obtain the compounds 5a, b. Phenyl (4-((Dimethylamino)methyl)phenyl)carbamate (5a) White solid; Yield: 82%; MS (ESI) m/z: 270.7 [M + H]+.

Molecular Weight:150.22
XLogP3:0.5
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:2
Exact Mass:150.115698455
Monoisotopic Mass:150.115698455
Topological Polar Surface Area:29.3
Heavy Atom Count:11
Complexity:104
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes