Reductive N-alkylation of nitro compounds to N -Alkyl and N, N -dialkyl amines with glycerol as the hydrogen source

Article abstract of DOI:10.1021/cs400049b

As the sustainable and promising hydrogen source, here, glycerol was directly used as the hydrogen source for the reductive amination of alcohol using nitrobenzene as the starting material. The amination of alcohols, especially aliphatic alcohols with different structures, was realized, and mono- or disubstituted amines were synthesized with excellent yields. The reaction mechanism was also explored.

Full text of DOI:10.1021/cs400049b

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Letter
Reductive N-Alkylation of Nitro Compounds to N-Alkyl
and N,N-Dialkyl Amines with Glycerol as Hydrogen Source
Xinjiang Cui, Youquan Deng, and Feng Shi
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/cs400049b • Publication Date (Web): 22 Mar 2013
Downloaded from http://pubs.acs.org on March 26, 2013
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Reductive N-Alkylation of Nitro Compounds to N-Alkyl and
N,N-Dialkyl Amines with Glycerol as Hydrogen Source
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*
Xinjiang Cui†,‡, Youquan Deng †and Feng Shi†
†Centre for Green Chemistry and Catalysis, Lanzhou institute of Chemical Physics, CAS, Lanzhou, 730000, China.
‡State Key Laboratory of Applied Organic Chemistry and Department of Chemistry, Lanzhou University, Lanzhou,
730000, China.
KEYWORDS: Amines, Alcohols, N-alkylation, Glycerol, Renewable, Catalysis
ABSTRACT: As the sustainable and promising hydrogen source, here glycerol was directly used as the hydrogen source
for the reductive amination of alcohol using nitro-
R
benzene as starting material. The amination of alco-
hols, especially aliphatic alcohols with different struc-
tures, was realized and mono- or di-substituted
amines were synthesized with excellent yields. The
reaction mechanism was also explored.
H
NO2
N
N
glycerol
[cat]
R
R
+
+ ROH
Renewable biomass has gained extensive attentions due
to the derivation of fuels and chemicals from petroleum
facing tremendous challenge for environmental and eco-
nomic sustainability.1 In the last years, many progresses
have been made in using biomass as carbon sources for
fuel and chemical production. Ethylene, ethanol, glycol,
glycerol and furan derivatives are all typical bio-based
feedstock.[2,3] Moreover, biomass or bio-based feedstock is
also a renewable source for the generation of CO and H2
through catalytic cracking or reforming.4-7 As a successful
example, recently, the hydrogen generation from glycerol
was reported.7-14 That means the bio-based feedstock
could be potential hydrogen source and it would be ideal
if bio-based feedstock could be directly used as reducing
agent in fine chemical synthesis without thermal cracking.
In this way, the carbon dioxide fixation in nature and the
fine chemical synthesis in industry could be put into one
carbon cycle and make a balance. However, till now, the
reports about fine chemical synthesis using bio-based
feedstock as hydrogen source is still less.15, 16Carbon-
nitrogen bonds are one of the key motifs in medicinal
agents and natural products.17,18 N-substituted amines are
usually prepared by the alkylation of amines with alkyl
halides.19,20 In many cases, N-substituted amines could
also be synthesized by hydroamination,21-23 hydroam-
inomethylation,24,25 and self-coupling of primary amine.26-
be synthesized using nitrobenzenes and alcohols as start-
ing materials.45-50 In this process, except its role as alkyla-
tion reagent, the alcohol was employed as the hydrogen
source to reduce nitrobenzene. Thus, large excess of alco-
hol was needed, in which the ratio of alcohol to nitroben-
zene is in the range of 6 : 1 to 10 : 1. It should be a good
choice if the coupling reaction could be realized with
equivalent amount of nitrobenzene and alcohol. Accord-
ing to the sustainable perspective, the incorporation of
biomass based feedstock as bydrogen source for this im-
portant transformation should be the ideal way.Based on
our effort in the clean and economic synthesis of N-
substituted amine using primary amine, nitrobenzene and
benzonitrile as starting materials, and alcohol as reducing
and alkylation reagent,49,51-54 we tried to develop a method
for the one-pot synthesis of N-substituted amines from
nitrobenzene with feedstock glycerol as the hydrogen
source. This system showed better generality than our
former report using Au/Ag-Mo catalyst.55
First, the catalytic activity of RuCl3/PPh3 was tested in
the presence of different solvents with K2CO3 as co-
catalyst, Table 1. Clearly, the solvent, ligand and base have
strong influence on the catalytic efficiency, entries 1-7.
The conversion was <50% in the absence of solvent, lig-
and or base. >95% conversion and selectivity of N-benzyl
aniline was obtained if using trifluoromethyl)benzene
(TFMB) as solvent possibly due to its suitable polarity and
boiling point. Further on, the activities of different ruthe-
nium complexes were tested but poor activity was ob-
served, entries 8-10. The conversion was 26-62% with 35-
28
In the last decades, many efforts have been focused on
the applying of alcohol as alkylation reagent due to its
intrinsic advantages such as easy availability, non-
expensiveness and low toxicity. So far, metal complexes
based on ruthenium, iridium, rhodium, gold, copper and
iron have been studied as catalysts for the coupling reac-
tion of amines and alcohols with excellent performance.29-
77%
selectivities
when
[Ru(p-cymene)Cl2]2,
[Ru(benzene)Cl2]2 and Ru3(CO)12 were employed although
they were reported to be active catalysts in N-substituted
44
Recently, it was shown that N-alkylated amines could
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Page 2 of 6
Table 1. Catalyst screening and reaction conditions
Table 2. Results for N-substituted amines synthesis
from different nitrobenzenes and alcoholsa
optimizationa
1
2
3
4
5
6
7
8
9
Entry Product
1
Yield Entry Product
(%)b
Yield
(%)b
86
11
80
90
87
Entry Catalyst
Solvent Ligand Conversion Selectivity
(%)b
(%)b
88
35
2
3
91
12
13
1
RuCl3
RuCl3
RuCl3
RuCl3
RuCl3
RuCl3
RuCl3
----
PPh3 50
(85c)
2
3c
4
5
6
7
8
TFMB ---
50
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
TFMB PPh3 17
TFMB PPh3 95
24
96
52
88
81
THF
PPh3 16
4
5
14
15
84
83
toluene PPh3 85
dioxane PPh3 24
65
56
35
[Ru(p-cymene) TFMB PPh3 26
83
Cl2]2
9
[Ru(benzene) TFMB PPh3 56
Cl2]2
77
6
7
8
9
76[d] 16
78
70
88
76
H
N
10
11
Ru3(CO)12
RuCl3
RuCl3
RuCl3
RuCl3
RuCl3
RuCl3
RuCl3
RuCl3
RuCl3
TFMB PPh3 62
TFMB DPPE 76
TFMB DPPP 70
TFMB DPPB 100
56
48
86
44
6
86
93
92
17
18
19
12
13
H
N
14
15
TFMB BPy
15
TFMB TMEDA56
TFMB Phen 37
TFMB PPh3 62
TFMB PPh3 70
TFMB PPh3 79
37
25
93
96
91
16
17d
18e
19f
10
86
20
85
a1.0 mmol nitrobenzene, 1.0 mmol benzylalcohol, 1.5 g
glycerol, 0.5 mL solvent, 2.5 mol% Ru, 10% mmol ligand, 10
mol% K2CO3, 130 Ar, 24 h.
oC,
TFMB=(trifluormethyl)benzene. THF=tetrahydrofuran.
PPh3=triphenylphosphine. DPPE=Ethylenebis (diphe-
nylphosphine). DPPP= 1,3-Bis(diphenylphosphino) propane.
DPPB=1,4-Bis(diphenyl phosphino) butane. BPy=2,2’-
bipyridine. TMEDA=N,N,N’,N’-Tetramethyl ethylenedia-
anitrobenzene (1.0 mmol), alcohol (1.0 mmol), glycerol (1.5
g), TFMB (0.5 mL), RuCl3 (2.5 mol%), PPh3 (10 mol%), K2CO3
(10 mol%), 130 oC, Ar, 24 h. bisolated yields. glycerol with
c
95% purity was used; d140 oC, 24 h.
The synthesis of N-substituted amines from nitroben-
zenes and alcohols with different structures were tested
to demonstrate the scope and generality of
RuCl3/PPh3/K2CO3 catalyst system. Generally, the catalytic
reactions were performed in the presence of 2.5 mol%
RuCl3, 10 mol% PPh3 and 10 mol% K2CO3 with 1 mmol ni-
b
c
d
mine. Phen=1,10-phenanthroline. By GC-MS. base free. 10
mol% KO-t-Bu. e10 mol% Na2CO3. f10 mol% KOH.
amine synthesis using alcohol or amine as alkylation rea-
gents.33, 40 Then, P- or N-containing ligands with different
structures were explored, entries 11-16. P-containing lig-
ands exhibited better catalytic performance than N-
containing ligands and PPh3. The application of other
bases such as KO-t-Bu, Na2CO3 and KOH resulted in low-
er nitrobenzene conversion but >90% selectivity main-
tained, entries 17-19. The major byproducts in above reac-
tions were all imine intermediates. If less glycerol was
employed (10 equiv), the conversion of the nitrobenzene
was 85% and selectivity to the corresponding product
decreased to 57%. Therefore, except its role as a reducing
agent, glycerol may behave as a co-solvent to promote the
transfer hydrogenation reaction.
o
trobenzene and 1 mmol alcohol at 130 C. As the results
shown in Table 2 various nitrobenzenes reacted with al-
cohols to give the desired products in good to excellent
yields. The coupling reaction of nitrobenzene and benzyl
alcohol proceeded smoothly with 86% isolated yield, en-
try 1. Next, nitroarenes with various functional groups
were further tested. For 4-methyl-nitrobenzene, 91% yield
was obtained, entry 2. 81-88% yields were achieved for
halide and methoxy containing nitrobenzenes, entries 3-5.
The reaction of benzyl alcohol with 2-nitronaphthalene
gave a good yield, too, entry 6. These results suggested
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hols. As a typical aliphatic alcohol containing aromatic
Table 3. Results for N,N-disubstituted amines syn-
thesis from nitrobenzenes and alcoholsa
1
2
ring, 2-phenylethanol was chosen as the starting material
first. To our delight, the isolated yield of 4-methyl-N-
phenethylaniline reached 90%, entry 12. In the following
tests, it was proved that linear or branched aliphatic alco-
hols with 4-10 carbons reacted with 4-methylnitrobenzene
to produce the corresponding mono-substituted amine
with 70-88% yields, entries 13-20. Meanwhile, similar re-
sult was obtained if glycerol with 95% purity was applied,
which suggested the practical potentialty of our method-
ology, entry 2, result in brackets.
3
4
5
6
Entry Product
1
YieldEntryProduct
(%)b
Yield
(%)b
81
85
9
7
8
9
10
11
12
13
14
15
16
17
18
19
20
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23
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2
3
86 10
82
89
In the reductive coupling reaction of nitrobenzenes
with 1 equivalent of alcohols, the formation of trace
amount of tertiary amines were also detectable. This re-
sult inspired us to try the one-pot synthesis of N,N-
disubstituted amines from nitrobenzenes with 2 equiva-
lents of alcohols. The results for the one-pot synthesis of
N,N-disubstituted amines were given in Table 3. Simply
increasing the reaction temperature to 150 oC, good to
excellent results were achieved, entries 1-8. The structure
and the position of the functional groups didn’t affect the
catalytic activity significantly and the yields of the desired
products were ~80%. The applying of aliphatic alcohols in
the coupling reactions gave 80-90% isolated yields no
matter linear or branched alcohols were used, entries 9-
16.
75 11
4
5
81 12
77
87
69 13
6
7
83 14
90
81
87 15
8
79 16
86
Scheme 1. A possible mechanism for the N-alkylation
reactions
anitrobenzene (1.0 mmol), alcohol (2.0 mmol), glycerol (1.5
g), solvent (0.5 mL), Ru (2.5 mol%), ligand (10 mol%), K2CO3
(10 mol%), 150 oC, Ar, 24 h. bisolated yields.
The exploration of the reaction mechanism should be
interesting. By tracing the coupling reaction of p-
methylnitrobenzene and benzyl alcohol by GC-MS, p-
toluidine was observed at the initial stage and then imine
was detectable. Subsequently, both p-toluidine and imine
were transformed into the N-substituted aniline, Scheme 1.
that the presence of functional groups on the aromatic
ring of the nitrobenzenes does not have inferior effect on
the catalytic activity. The variation of molecular structure
of alcohols doesn’t affect the progress of the reaction, too.
The reductive coupling of 4-methylnitrobenzene with
benzylic alcohols containing different substituting groups
including methyl, methoxy, isopropyl, methylthio and
chlorine gave 80-93% isolated yields, entries 7-11. One of
the challenging operation in the alcohol amination reac-
tions is that using aliphatic alcohols as alkylation rea-
gents. For example, in recent report, the reductive cou-
pling reactions of nitrobezenes with alcohols using mo-
lecular hydrogen as reducing reagent was restricted to
benzylic acohols.56 Thus here we focused on the reductive
coupling reactions of nitrobenzenes with aliphatic alco-
1
In order to check the oxidation product of glycerol, H
NMR and LC-MS characterizations were performed. Ac-
1
cording to H NMR characterization, the signals at 10.05
ppm for benzladehyde and at 9.64 ppm for glycerol alde-
hyde could be observed. Based on LC-MS characterization,
the oxidation product of glycerol could be observed, i.e.
glyceraldehyde, too ([glyceraldehyde·Cl]-, m/z = 125.1).
Therefore the oxidation product of glycerol occurred on
the terminal hydroxyl group and a portion of alcohol was
oxidized into the corresponding aldehyde. Next, the p-
toluidine will react with aldehyde to generate N-
benzylidene-4-methylaniline and N-alkyl amine was pro-
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ASSOCIATED CONTENT
Supporting Information. The reaction procedures and
characterization results of products were given in the sup-
porting information. This material is available free of charge
via the internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*fshi@licp.cas.cn.
ACKNOWLEDGMENT
The research was supported by Natural Science Foundation
of China (21073208) and Chinese Academy of Sciences.
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