Photochemical Synthesis of Aminoalkylanilines
39.5 ppm, as well as between CH-2′ at 59.3 ppm and the
benzylic hydrogens (2.6-2.75 ppm), were evidenced. In the
case of compound 11a , the aromatic ring and the amine were
bonded to the same carbon in the hexane chain. Thus, CH-1′
(62.8 ppm) gave a cross-peak with the aromatic hydrogens
at 7.05 ppm as well as with the amine methylene group at
2.45 ppm; H-1′ at 3.45 ppm gave a cross-peak with CH2N at
47.3 ppm. Anal. Found: C, 77.9; H, 11.8; N, 10.1. Calcd for
27.9 (CH2), 32.2 (CH2), 33.3 (CH2), 39.6 (CH2-1), 46.7 (CH2-
N), 59.3 (CH-2), 115.2 (CH), 129.5, 129.9 (CH),144.3. GC-MS
m/z 248.
4-[1-(Bu t yla m in om et h yl)p en t yl]-a n ilin e (10b ). Anal.
Found: C, 77.2; H, 11.4; N, 11.2. Calcd for C16H28N2: C, 77.36;
1
H, 11.36; N, 11.28. H NMR δ (CDCl3) 0.85 (t, J ) 7 Hz, 3H),
0.95 (t, J ) 7 Hz, 3H), 1.2-1.7 (m, 10H), 2.4-2.6 (m, 2H,),
2.65 (m, 1H, H-2), 2.7-2.8 (m, 2H), 3.5 (broad, 2H, NH2), 6.65
and 6.98 (AA′BB′, 4H); 13C NMR δ (CDCl3) 13.8 (CH3), 14.0
(CH3), 20.3 (CH2), 22.6 (CH2), 29.5 (CH2), 31.6 (CH2), 34.4
(CH2), 44.7 (CH), 49.3 (CH2), 57.7 (CH2N), 115.3 (CH), 128.4
(CH), 133.5, 144.6. GC-MS m/z 248.
C
18H32N2: C, 78.20; H, 11.67; N, 10.13. Da ta for 9a :1H NMR
(CDCl3) δ 0.87 (t, 3H, J ) 7 Hz), 0.9 (t, 3H, J ) 7 Hz), 1.2-1.5
(m, 10H), 2.5-2.7 (m, 2H), 2.6-2.75 (m, 2H, H-1), 2.8 (m, 1H,
H-2), 2.93 (s, 6H), 6.65 and 7.01 (AA′BB′, 4H); 13C NMR
(CDCl3) δ 13.9 (CH3), 14.0 (CH3), 20.3 (CH2), 22.9 (CH2), 28.0
(CH2), 32.3 (CH2), 33.4 (CH2), 39.5 (CH2-1), 40.7 (NCH3), 46.8
(CH2N), 59.3 (CH-2), 112.8 (CH), 127.8, 129.8 (CH), 149.1.
Da ta for 11a :1H NMR δ (CDCl3) 0.87 (t, J ) 7 Hz, 3H), 0.9 (t,
J ) 7 Hz, 3H), 1.25-1.75 (m, 12H), 2.45 (t, J ) 7 Hz, 2H,
CH2N), 2.98 (s, 6H), 3.45 (dd, J ) 8, 6 Hz, 1H, H-1), 6.7 and
7.05 (AA′BB′, 4H); 13C NMR δ (CDCl3) 13.95 (CH3), 13.98
(CH3), 20.4 (CH2), 22.5 (CH2), 26.1 (CH2), 31.8 (CH2), 32.3
(CH2), 38.1 (CH2), 40.6 (NCH3), 47.3 (CH2N), 62.8 (CH-1), 112.5
(CH), 127.8 (CH), 132.5, 149.5.
4-(2-P ip er id in oh exyl)a n ilin e (12b). Anal. Found: C, 78.5;
H, 10.8; N, 10.6. Calcd for C17H28N2: C, 78.40; H, 10.84; N,
1
10.76. H NMR (CDCl3) δ 0.85 (t, 3H, J ) 7 Hz), 1.1-1.7 (m,
12H), 2.25 (dd, 1H, J ) 13.5, 8.5 Hz, H-1), 2.4-2.7 (m, 4H,
CH2N), 2.55 (m, 1H, H-2), 2.85 (dd, 1H, J ) 13, 4.5, H-1), 3.5
(broad, 2H, exch, NH2), 6.6 and 6.95 (AA′BB′, 4H); 13C NMR δ
(CDCl3) 13.9 (CH3), 22.6 (CH2), 24.9 (CH2), 26.3 (CH2), 29.2
(CH2), 30.0 (CH2), 34.7 (CH2-1), 49.5 (CH2N), 66.9 (CH-2), 115.0
(CH), 129.8 (CH), 131.5, 143.8. GC-MS m/z 260.
4-(1-P ip er id in om eth yl)p en tyl)a n ilin e (13b). Anal.
N ,N -D i m e t h y l-4-[1-(b u t y la m i n o m e t h y l)p e n t y l]-
a n ilin e (10a ). Anal. Found: C, 78.0; H, 11.7; N, 10.0. Calcd
for C18H32N2: C, 78.20; H, 11.67; N, 10.13. 1H NMR (CDCl3) δ
0.85 (t, 3H, J ) 7 Hz), 0.9 (t, 3H, J ) 7 Hz), 1.1-1.65 (m,
10H), 2.4-2.6 (m, 2H), 2.7 (m, 1H, H-1), 2.7-2.9 (m, 2H), 2.95
(s, 6H), 6.7 and 7.05 (AA′BB′, 4H); 13C NMR (CDCl3) δ 13.9
(CH3), 14.0 (CH3), 20.4 (CH2), 22.6 (CH2), 29.6 (CH2), 32.0
(CH2), 34.4 (CH2), 40.6 (NCH3), 44.7 (CH-1), 49.6 (CH2N), 56.0
(CH2N), 112.8 (CH), 128.2 (CH), 131.8, 149.1.
Found: C, 78.4; H, 11.0; N, 10.6. Calcd for C17H28N2: C, 78.40;
H, 10.84; N, 10.76. H NMR (CDCl3) δ 0.9 (t, 3H, J ) 7 Hz),
1
1.1-1.8 (m, 12H), 2.25-2.4 (m, 4H, CH2N), 2.4 and 2.5 (AB
part, 2H, J ) 12.5 Hz), 2.7 (m,1H, H-1), 3.5 (broad, exch, NH2),
6.7 and 6.95 (AA′BB′, 4H); 13C NMR (CDCl3) δ 13.9 (CH3), 22.7
(CH2), 24.4 (CH2), 25.8 (CH2), 29.6 (CH2), 34.2 (CH2), 42.5 (CH-
1), 54.9 (CH2N), 66.3 (CH2), 115.1 (CH), 128.4 (CH), 135.2,
144.2. GC-MS m/z 260.
N ,N -D im e t h y l-4-(t r a n s-2-b u t y la m in o c y c lo h e x y l)-
a n ilin e (15a ). Anal. Found: C, 78.8; H, 11.1; N, 10.2 Calcd
for C18H30N2: C, 78.77; H, 11.02; N, 10.21. 1H NMR (CDCl3) δ
0.85 (t, 3H, J ) 7 Hz), 1.1-2.1 (m, 12H), 2.3 and 2.63 (m, 2H),
2.35 (dt, 1H, J ) 3, 10 Hz, H-2), 2.55 (dt, 1H, J ) 3, 10 Hz,
H-1), 2.95 (s, 6H), 6.7 and 7.1 (AA′BB′, 4H). The large coupling
constants between H-1′ and H-2′ (10 Hz) proved their trans
spatial relationship. 13C NMR (CDCl3) δ 13.7 (CH3), 20.2 (CH2),
25.2 (CH2), 26.5 (CH2), 32.0 (CH2), 32.1 (CH2), 34.8 (CH2), 40.6
(NMe), 46.7 (CH2N), 49.8 (CH-2), 61.4 (CH-1), 113.0 (CH),
128.1 (CH), 132.1, 149.3.
N,N-Dim eth yl-4-(2-p ip er id in oh exyl)a n ilin e (12a ). Anal.
Found: C, 78.9; H, 11.2; N, 9.6. Calcd for C19H32N2: C, 79.11;
H, 11.18; N, 9.71.1H NMR (CDCl3) δ 0.85 (t, 3H, J ) 7 Hz),
1.2-1.6 (m, 12H), 2.25 (dd, 1H, J ) 13, 8.5 Hz, H-1), 2.45-
2.74 (m, 4H, CH2N), 2.65 (m, 1H, H-2), 2.89 (dd, 1H, J ) 13,
4.5 Hz, H-1), 2.95 (s, 6H), 6.7 and 7.05 (AA′BB′, 4H); 13C NMR
(CDCl3) δ 14.0 (CH3), 22.7 (CH2), 25.1 (CH2), 26.6 (CH2), 29.2
(CH2), 30.1 (CH2), 34.4 (CH2-1), 40.8 (NMe), 49.5 (CH2N), 66.9
(CH-2), 112.8 (CH), 129.6 (CH), 130.1, 148.7. GC-MS m/z 288.
N,N-Dim et h yl-4-[(1-p ip er id in om et h yl)p en t yl)a n ilin e
(13a) and N,N-dim eth yl-4-(1-piper idin oh exyl)an ilin e (14a)
were obtained as a mixture to which the NMR characterization
and elemental analysis are referred. The former was the main
one. As for the similar compounds isolated with butylamine,
the structure was attributed on the basis of HSQC and HMBC
2D NMR spectra. In particular in the case of 14a the aromatic
hydrogen at 7.05 ppm gave a long-range correlation with CH-
1′ at 69.8 ppm, which in turn gave a cross-peak with piperidine
hydrogens at 2.4 ppm. For 13a the expected correlations were
observed. Anal. Found: C, 79.0; H, 11.3; N, 9.7. Calcd for
N,N-Dim eth yl-4-[(1-bu tyla m in o-1cyclop en tyl)m eth yl]-
a n ilin e (16a ). 2D-TOCSY (120 ms as mixing time) and
NOESY supported the structure attribution. In detail, the first
experiment identified the proton signals of a buthylamino
fragment (2.4, 1.45, 1.3 and 0.85 ppm) and of cyclopentylm-
ethyl moiety (3.12, 2.1, 1.95, 1.6, 1.35 and 1.1 ppm). The NOE
correlations found in NOESY experiment between the aromat-
ics at 7.1 ppm and hydrogens at 3.12, 2.1 2.4 ppm confirmed
that butylamine and aniline were bonded to the same hexane
carbon. Anal. Found: C, 78.6; H, 11.1; N, 10.0. Calcd for
19H32N2: C, 79.11; H, 11.18; N, 9.71. Da ta for 13a : 1H NMR
C
18H30N2: C, 78.77; H, 11.02; N, 10.21. 1H NMR (CDCl3) δ 0.85
C
(CDCl3) δ 0.85 (t, 3H, J ) 7 Hz), 1.1 (sext, 2H, J ) 7 Hz),
1.2-1.85 (m, 10H), 2.25-2.45 (m, 4H, -CH2-N), 2.35 and 2.5
(AB part, 2H, J ) 13 Hz), 2.7 (m, 1H, H-1), 2.95 (s, 6H), 6.7
and 7.05 (AA′BB′, 4H); 13C NMR (CDCl3) δ 14.0 (CH3), 22.8
(CH2), 24.5 (CH2), 26.0 (CH2), 26.3 (CH2), 29.8 (CH2), 34.1
(CH2), 40.8 (NCH3), 42.3 (CH-1), 55.1 (CH2N), 66.5 (CH2), 112.9
(CH), 128.2 (CH), 133.3, 148.8. Da ta for 14a : 1H NMR δ
(CDCl3) 0.85 (t, 3H, J ) 7 Hz), 1.1-1.65 (m, 14H), 2.4 (m, 4H,
CH2N), 2.98 (s, 6H), 3.12 (dd, 1H, J ) 9, 4.5 Hz, H-1), 6.7 and
7.05 (AA′BB′, 4H); 13C NMR (CDCl3) δ 14.0 (CH3), 22.5 (CH2),
24.6 (CH2), 26.0 (CH2), 26.5 (CH2), 32.0 (CH2), 32.6 (CH2), 40.5
(NCH3), 50.6 (CH2N), 69.8 (CH-1), 111.8 (CH), 127.8, 129.5
(CH), 149.5.
(t, 3H, J ) 7 Hz), 1.05-1.9 (m, 12H), 2.1 (m, 1H), 2.4 (m, 2H),
2.95 (s, 6H), 3.12 (d, 1H, J ) 9 Hz, H-1), 6.7 and 7.1 (AA′BB′,
4H); 13C NMR (CDCl3) δ 13.8 (CH3), 20.3 (CH2), 24.8 (CH2),
25.3 (CH2), 30.2 (CH2), 30.6 (CH2), 32.0 (CH), 40.5 (NMe), 47.2
(CH2), 47.3 (CH), 68.3 (CH-1), 112.2 (CH), 128.2 (CH), 131.8,
149.4.
N ,N -D i m e t h y l-4-(t r a n s-2-p i p e r i d i n o c y c lo h e x y l)-
a n ilin e (17a ). In the carbon spectrum, the cyclohexane CH-1
and CH-2 were clearly distinguished (68.1 and 46.8 ppm),
while the 1H-13C correlations (HSQC experiment) showed that
both H-1′ and H-2′ appeared in the proton spectrum at 2.6
ppm, superimposed with two piperidine hydrogens. Their trans
spatial relationship was attributed by comparison with the
analogue compounds obtained with butylamine (15b and 15a ).
Anal. Found: C, 79.6; H, 10.7; N, 9.7. Calcd for C19H30N2: C,
79.66; H, 10.56; N, 9.78. 1H NMR (CDCl3) δ 1.22-1.4 (m, 10H),
1.7-2.0 (m, 4H), 2.2 and 2.6 (m, 4H, CH2N), 2.6 (m, 2H), 2.95
(s, 6H, NMe2), 6.7 and 7.1 (AA′BB′, 4H); 13C NMR (CDCl3) δ
25.1 (CH2), 26.3 (CH2), 26.4 (CH2), 26.5 (CH2), 26.7 (CH2), 36.4
4-(2-Bu tyla m in oh exyl)a n ilin e (9b). Anal. Found: C, 77.3;
H, 11.4; N, 11.2. Calcd for C16H28N2: C, 77.36; H, 11.36; N,
1
11.28. H NMR (CDCl3) δ 0.88 (t, 3H, J ) 7 Hz), 0.9 (t, 3H, J
) 7 Hz), 1.2-1.5 (m, 10H), 2.5-2.7 (m, 5H, H-1, H-2 and
CH2N)), 3.5 (broad, 2H, NH2), 6.6 and 6.9 (AA′BB′, 4H); 13C
NMR (CDCl3) δ 13.8 (CH3), 14.0 (CH3), 20.3 (CH2), 22.9 (CH2),
J . Org. Chem, Vol. 68, No. 3, 2003 1073