One-Pot Reductive Monoalkylation of Nitro Aryls Using Aromatic Aldehydes with H2 Over Pd/Sio2

One-pot Reductive Monoalkylation of Nitro Aryls Using Aromatic Aldehydes with H2 over Pd/SiO2

Hui Li·Zhengping Dong·Pan Wang·Fengwei Zhang·Jiantai Ma

State Key Laboratory of Applied Organic Chemistry, Lanzhou, 730000, People’s Republic of China

College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, People’s Republic of China

*Corresponding author. Tel/fax: +86-931-8912577.

E-mail address: (Jiantai Ma).

Supporting Information

Title and table of contents ………………………………………………………………..1

Experimental procedure…………………………………………………………………..2-3

Compound data……………………………………………………………………………3-5

Copies of MS spectra……………………………………………………………………...5-22

1. Experimental procedure

Reaction of nitrobenzene and benzaldehyde: optimization of the reaction conditions

Table 1 N-alkylation of nitrobenzene with benzaldehyde catalyzed by Pd/SiO2 under H2 atmosphere and various temperature a.

a The reaction was carried out with nitrobenzene (0.5 mmol), benzaldehyde (0.75 mmol), and Pd/SiO2 (20 mg, 15 wt %) in aqueous ethanol (5 ml) for 10 h.

b Determined by GC.

Table 2 N-alkylation of nitrobenzene with benzaldehyde catalyzed by Pd/SiO2 under H2 atmosphere and various reaction time a.

a The reaction was carried out with nitrobenzene (0.5 mmol), benzaldehyde (0.75 mmol), and Pd/SiO2 (20 mg, 15 wt %) in aqueous ethanol (5 ml) at 40 oC.

b Determined by GC-MS.

Table 3 N-alkylation of nitrobenzene with benzaldehyde catalyzed by Pd/SiO2 under H2 atmosphere and in various solventsa

a The reaction was carried out with nitrobenzene (0.5 mmol), benzaldehyde (0.75 mmol), and Pd/SiO2 (20 mg, 15 wt %) in aqueous alcoholic solvents (5 ml) at 40 oC for 10 h.

b Determined by GC-MS

2. Compounds data

3a N-benzylaniline (Table 1, entry 1, Table 2, entry 8 and Table 3, entry 10, commercially available)

3b N-(3, 5-dimethoxybenzyl)aniline (Table 2, entry 1). MS (EI) 243 (M+)

3c 2-methoxy-4-((phenylamino)methyl)phenol (Table 2, entry 2). MS (EI) 229 (M+)

3d N-(3,4-dimethoxybenzyl)aniline (Table 2, entry 3). MS (EI) 243 (M+)

3e N-(4-methoxybenzyl)aniline (Table 2, entry 4). MS (EI) 213 (M+)

3f 4-((phenylamino)methyl)benzene-1,3-diol (Table 1, entry 5). MS (EI) 215 (M+)

3g 3-((phenylamino)methyl)phenol (Table 1, entry 6). MS (EI) 199 (M+)

3h N-(4-chlorobenzyl)aniline (Table 1, entry 7). MS (EI) 217 (M+)

3i N-benzyl-2-methylaniline (Table 3, entry 1). MS (EI) 197 (M+)

3o N-benzyl-4-chloroaniline (Table 3, entry 7). MS (EI) 217 (M+)

3r N-ethyl-4-methylaniline (Scheme 1) MS (EI) 135 (M+)

6 N-benzylidene-4-methoxyaniline (Scheme 2) MS (EI) 211 (M+)

8a N-benzylidenenaphthalen-2-amine (Table 4, entry 1). MS (EI) 231 (M+)

9a N-benzylnaphthalen-2-amine (Table 3, entry 1). MS (EI) 233 (M+)

8b N-(4-methoxybenzylidene)naphthalene-2-amine (Table 3, entry 2). MS (EI) 261 (M+)

9b N-(4-methoxybenzyl)naphthalene-2-amine (Table 3, entry 2b). MS (EI) 263 (M+)

8c 4-((naphthalene-2-ylamino)methyl)phenol (Table 3, entry 3a). MS (EI) 247 (M+)

3. Copies of MS spectra