204
SIVCEV et al.
8
2
NH2
NH2
1
NH2
1
NO2
7
8
7
10
O
7
9
2
6
9
NH
1
2
3
2
+
+
+
10
5
HO
3
3
6
4
(8)
(9)
(10)4
9
3
5
O
8
4
(11)
(12)
10
Scheme 2. Conversions of oꢀnitrotoluene (8) in scꢀiPrOH.
C6), 153.20 s (C2), 111.51 d (C3) 125.49 d (C4), 121.49 s (С1), 145.35 s (C2), 114.73 d (C3), 127.84 s (C4),
d (C5), 49.16 d (C7), 23.10 q (C8, C9), 17.52 q (C10).
The products (0.11 g) obtained via the reduction of
121.29 d (C5), 115.26 d (C6), 70.62 d (C7), 22.26 q (C8,
C9), 20.83 q (C10).
m
ꢀnitrotoluene (13) were separated into 2ꢀisoproꢀ
poxyꢀ5ꢀmethylaniline (15, 0.013 g) and 2ꢀisoproꢀ ppm: 1.19 d (C8H3
poxyꢀ ꢀisopropylꢀ5ꢀmethylaniline (17, 0.024 g).
Compound 15. 1H NMR spectrum (CDCl3),
ppm: 1.31 d (C8H3 C9H3
J8(9),7 = 6.1 Hz), 2.20 s
C10H3), 4.43 septet (H7, J7,8(9) = 6.1 Hz), 6.47 ddq
H4,
4,3 = 8.1 Hz, 4,6 = 2.2 Hz, J4,10 = 0.7 Hz), 6.53 d
H6, J6,4 = 2.2 Hz), 6.67 d (H3, J3,4 = 8.1 Hz). 13C
Compound 22. 1H NMR spectrum (CDCl3),
,
δ
,
C9H3
C11H3, C12H3, J11(12),10 = 6.1 Hz), 2.22 s (C13H3), 3.55
, J8(9),7 = 6.3 Hz), 1.32 d
N
(
septet (H7, J7,8(9) = 6.3 Hz), 4.47 septet (H10, J10,11(12)
6.1 Hz), 6.51 d (H6, J6,5 = 8.1 Hz), 6.60 bd (H3, J3,5
=
=
δ
,
,
,
1.8 Hz), 6.63 ddq (H5, J5,6 = 8.1 Hz, J5,3 = 1.8 Hz,
(
(
(
J5,13 = 0.7 Hz). 13C NMR spectrum (CDCl3),
, ppm:
δ
J
J
136.20 s (С1), 144.99 s (C2), 114.20 d (C3), 125.33 s
(C4), 121.35 d (C5), 111.07 d (C6), 44.26 d (C7),
23.00 q (C8, C9), 70.82 d (С10), 22.27 q (С11, С12),
20.72 q (C13).
NMR spectrum (CDCl3),
δ
, ppm: 137.15 s (С1),
138.54 s (C2), 114.10 d (C3), 118.59 d (C4), 130.65 s
(C5), 116.14 d (C6), 70.92 d (C7), 22.23 q (C8, C9),
20.62 q (C10).
Compound 17. 1H NMR spectrum (CDCl3),
,
δ
RESULTS AND DISCUSSION
ppm: 1.21 d (C8H3
C11H3, C12H3, J11(12),10 = 6.1 Hz), 2.25 s (C13H3), 3.59
septet (H7, J7,8(9) = 6.3 Hz), 4.42 septet (H10, J10,11(12)
6.1 Hz), 6.38 ddq (H4,
4,3 = 8.1 Hz, 4,6 = 2.2 Hz, J4,13
= 0.7 Hz), 6.43 d (H6, J6,4 = 2.2 Hz), 6.66 d (H3, J3,4
, , J8(9),7 = 6.3 Hz), 1.31 d
C9H3
In studying the processes that occur during the
(
reduction of nitrobenzene (
reactor in supercritical alcohols, we found [5] that the
reaction mixture contained products of ꢀalkylation
), alkoxylation ( and ), and both these processes (
and ) in addition to aniline ( ), a key product, indeꢀ
1) over Al2O3 in a flow
=
J
J
N
=
8.1 Hz). 13C NMR spectrum (CDCl3),
, ppm: 138.41
δ
(
3
4
5
6
s (С1), 142.73 s (C2), 113.33 d (C3), 115.86 d (C4),
130.75 s (C5), 111.64 d (C6), 43.84 d (C7), 23.01 q (C8,
C9), 71.14 d (C10), 22.26 q (C11, C12), 21.12 q (C13).
7
2
pendently of the composition of the supercritical solꢀ
vent and the reaction temperature (Scheme 1). It
seems that compounds
of intermediately formed iminium cations
with isopropanol. This route of the formation of comꢀ
pounds was confirmed by the absence of alkoxyꢀ
lation products for aniline allowed to stand under
4
and
5
result from the reaction
The products (0.10 g) obtained via the reduction of
ꢀnitrotoluene 19 were separated into 2ꢀisopropoxyꢀ
A
and
B
p
4ꢀmethylaniline (21, 0.005 g) and 2ꢀisopropoxyꢀ
isopropylꢀ4ꢀmethylaniline (22, 0.011 g).
Nꢀ
4–7
2
Compound 21. 1H NMR spectrum (CDCl3),
,
δ
reaction conditions [5]. It was noteworthy that introꢀ
ducing a halide atom into the aromatic ring almost
completely blocked the process of alkoxylation [5].
ppm: 1.33 d (C8H3 C9H3
, , J8(9),7 = 6.1 Hz), 2.23 s
(
C10H3), 3.60 bs (NH2), 4.49 septet (H7, J7,8(9)
6.1 Hz), 6.56 ddq (H5,
5,6 = 7.8 Hz, 5,3 = 1.7 Hz, J5,10
0.7 Hz), 6.60 d (H6, J6,5 = 7.8 Hz), 6.61 bd (H3, J3,5
1.7 Hz). 13C NMR spectrum (CDCl3),
=
=
=
J
J
We began our study of the conversion of nitrotoluꢀ
enes with
was 2% at 270
only product (Table 1). After the temperature was raised
to 300 , conversion grew to 20%, and the selectivity to
ꢀtoluidine ( ) reached 66%. It should be noted that the
conversion of nitrobenzene under the same conditions
was slightly higher [5] than for ꢀnitrotoluene. Comparꢀ
ing the conversions of ꢀchloronitrobenzene [5] and
ꢀnitrotoluene ( ) under the same conditions, we may
conclude that orthoꢀhalogenated nitrobenzene is more
reactive than ꢀnitrotoluene.
o
ꢀnitrotoluene (
8
, Scheme 2). Conversion
δ
, ppm: 134.65
°C
, and ꢀtoluidine (
о
9) proved to be the
°C
Table 1. Conversion of
oꢀnitrotoluene (8) in scꢀiPrOH
о
9
Selectivity, %
Converꢀ
sion, %
T, °C
о
9
10
11
12
о
270
300
320
2
20
100
100
66
62
–
12
13
–
13
12
–
9
13
о
8
o
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
Vol. 89
No. 2 2015