1128 J . Org. Chem., Vol. 64, No. 4, 1999
Alajar´ın et al.
1H, J ) 8.6, 1.1 Hz), 7.33-7.46 (m, 9H), 7.68-7.79 (m, 6H);
13C NMR (CDCl3) δ 55.3, 55.6, 102.1, 110.2 (d, 3J C-P ) 7.6 Hz),
(CDCl3) δ 40.7, 40.8, 112.8, 113.1, 117.6, 120.4, 124.6, 124.7,
125.2, 125.7, 127.3, 128.3, 128.7, 128.7, 131.1, 131.2, 132.6,
133.3, 140.4, 142.8, 144.2, 148.1, 152.2, one quaternary carbon
atom was not observed; mass spectrum m/z (relative intensity)
472 (M+, 9), 280 (100). Anal. Calcd for C30H28N6: C, 76.24; H,
5.97; N, 17.78. Found: C, 76.40; H, 5.75; N, 17.85.
3
4
111.8, 128.3 (d, J C-P ) 11.9 Hz), 131.2 (d, J C-P ) 2.8 Hz),
1
2
132.4 (d, J C-P ) 100.1 Hz), 132.4 (d, J C-P ) 9.8 Hz), 141.5
(d, 2J C-P ) 2.4 Hz), 147.5 (d, 3J C-P ) 2.9 Hz), 154.1 (d, 4J C-P
)
1.7 Hz); mass spectrum m/z (relative intensity) 413 (M+, 23),
183 (100). Anal. Calcd for C26H24NO2P: C, 75.53; H, 5.85; N,
3.39. Found: C, 75.40; H, 5.69; N, 3.53.
[a ,c]Bis[d iben zo[d ,f][1,3]d ia zep in o]-1,3-d ia zetid in e (6):
2-6% yield; mp 324-325 °C; colorless prisms (dichloromethane);
1
Gen er a l P r oced u r e for th e P r ep a r a tion of 1-Ar yl-2-
ar ylim in odiben zo[d,f]-1,3-diazetidin o[1,2-a ]diazepin es (2).
Meth od A. To a solution of 2,2′-bis(isothiocyanato)biphenyl
(4) (0.35 g, 1.3 mmol) in 30 mL of dry benzene was added the
corresponding aryliminophosphorane 5 (2.6 mmol). The reac-
tion mixture was stirred and heated at reflux temperature
under nitrogen for 8-20 h. The solvent was removed under
reduced pressure, and the remaining material was chromato-
graphed on a silica gel column using the appropriate eluent.
By this procedure, the following compounds (2a -e) were
prepared, and the diazetidine 6 was also isolated in low yield
(2-6%):
1-(4-Tolyl)-2-(4-tolyl)im in od iben zo[d ,f]-1,3-d ia zetid in o-
[1,2-a ]d ia zep in e (2a ): silica gel, n-hexane/dichloromethane
7:3; 37% yield; mp 184-186 °C; colorless prisms (n-hexane);
IR (Nujol) 1687 cm-1; 1H NMR (CDCl3) δ 2.28 (s, 3H), 2.33 (s,
3H), 6.27-6.48 (m, 1H), 7.00-7.44 (m, 13H), 7.84-8.05 (m,
2H); 13C NMR (CDCl3) δ 20.2, 21.1, 117.3, 118.8, 123.2, 124.9,
125.7, 127.6, 128.2, 128.7, 128.9, 129.5, 130.0, 131.2, 131.5,
132.7, 133.3, 134.5, 134.8, 141.4, 141.7, 142.2, 143.8, 151.3;
mass spectrum m/z (relative intensity) 414 (M+, 5) 222 (100).
Anal. Calcd for C28H22N4: C, 81.13; H, 5.35; N, 13.52. Found:
C, 81.00; H, 5.46; N, 13.54.
1-(2,4-Dim eth oxyp h en yl)-2-(2,4-d im eth oxyp h en yl)im i-
n odiben zo[d,f]-1,3-d ia zetidin o[1,2-a ]d ia zep in e (2b): silica
gel, n-hexane/dichloromethane 1:1; 62% yield; mp 121-122 °C;
colorless prisms (ethanol); IR (Nujol) 1702, 1681 cm-1; 1H NMR
(CDCl3) δ 3.58 (s, 9H), 3.64 (s, 3H), 6.37-6.73 (m, 6H), 7.07-
7.29 (m, 6H), 7.39-7.46 (m, 2H); 13C NMR (CDCl3) δ 55.7, 55.8,
55.9, 56.0, 108.9, 109.9, 111.6, 112.1, 113.7, 115.3, 116.0, 122.2,
124.9, 125.6, 127.6, 127.9, 128.7, 128.8, 131.2, 131.7, 132.9,
133.8, 142.9, 143.8, 144.2, 145.3, 149.2, 152.1, 153.0, 153.3;
mass spectrum m/z (relative intensity) 506 (M+, 9), 314 (100).
Anal. Calcd for C30H26N4O4: C, 70.85; H, 5.55; N, 11.02.
Found: C, 70.64; H, 5.37; N, 10.93.
IR (Nujol) 1708 cm-1; H NMR (CDCl3) δ 7.12-7.44 (m, 7H),
7.96 (dd, 1H, J ) 8.0, 1.3 Hz); 13C NMR (CDCl3) δ 115.9, 125.8,
126.8, 127.9, 128.8, 129.0, 129.2, 131.4, 132.0, 133.1, 142.0,
143.6, 149.1; mass spectrum m/z (relative intensity) 384 (M+,
11), 192 (100). Anal. Calcd for C26H16N4: C, 81.23; H, 4.19; N,
14.57. Found: C, 81.37; H, 3.95; N, 14.68.
Meth od B. To a solution of 2,2′-bis[(triphenylphosphora-
nylidene)amino]biphenyl (1) (0.55 g, 0.78 mmol) in 25 mL of
dry benzene was added the corresponding aryl isocyanate (1.6
mmol). The resulting mixture was heated at reflux tempera-
ture under nitrogen for 8-20 h. The solvent was removed
under reduced pressure, and the residual material was chro-
matographed on a silica gel column with n-hexane/dichlo-
romethane 7:3 as eluent. Using this procedure the following
compounds were prepared:
2a : 40% yield.
2d : 22% yield.
2,2′-B is [N -(4-m e t h o x y p h e n y l)t h io u r e id o -N ′-y l]b i-
p h en yl (7c). 4-Methoxyaniline (0.46 g, 3.72 mmol) was added
to a solution of 2,2′-bis(isothiocyanato)biphenyl (0.5 g, 1.86
mmol) in 20 mL of dry dimethylformamide. The resulting
mixture was stirred at room temperature under nitrogen for
12 h. Then, the reaction mixture was poured into water/ice,
and the precipitated solid was collected by filtration, air-dried,
and recrystallized from chloroform to give 7: 87% yield; mp
191-193 °C; colorless prisms (chloroform); IR (Nujol) 3159,
1
1520 cm-1; H NMR (CDCl3) δ 3.74 (s, 6H), 6.71 (d, 4H, J )
9.0 Hz), 6.80 (d, 4H, J ) 9.0 Hz), 7.15 (dd, 2H, J ) 7.6, 1.4
Hz), 7.27 (t, 2H, J ) 7.8 Hz), 7.41 (td, 2H, J ) 7.6, 1.6 Hz),
7.56 (s, broad, 2H), 7.74 (d, 2H, J ) 7.8 Hz), 8.12 (s, broad,
2H); 13C NMR (CDCl3) δ 55.5, 115.0, 126.7, 127.8, 128.2, 128.3,
128.4, 130.1, 134.9, 136.8, 158.9, 180.6; mass spectrum m/z
(relative intensity) 268 (9), 108 (100). Anal. Calcd for
C
28H26N4O2S2: C, 65.35; H, 5.09; N, 10.89. Found: C, 65.18;
H, 5.22; N, 11.02.
1-(4-Meth oxyp h en yl)-2-(4-m eth oxyp h en yl)im in od iben -
zo[d ,f]-1,3-d ia zetid in o[1,2-a ]d ia zep in e (2c): silica gel, n-
hexane/dichloromethane 1:1; 53% yield; mp 162-164 °C;
2-[4-(Met h oxyp h en yl)a m in o]d ib en zo[d ,f][1,3]d ia ze-
p in e (8c). This compound was obtained from the dehydrosul-
furization reactions of the bis(thiourea) 7c employing proce-
dures a and c, which will be described in the following text
for the dehydrosulfurization of the bis(thiourea) 22. After
chromatography (silica gel, n-hexane/ethyl acetate 1:1), the
guanidine 8c (45 and 21% yield, respectively) and 4-methox-
yphenyl isothiocyanate were isolated. 8c: 45% yield; mp 244-
245 °C; colorless prisms (chloroform); IR (Nujol) 3348, 1665
cm-1; 1H NMR (CDCl3) δ 3.81 (s, 3H), 6.89-6.93 (m, 6H), 7.14-
7.31 (m, 6H), 7.47 (dd, 2H, J ) 7.3, 1.8 Hz); 13C NMR (CDCl3)
δ 55.1, 115.1, 120.6, 124.1, 124.7, 128.8, 129.4, 130.6, 140.5,
155.9, 157.9; mass spectrum m/z (relative intensity) 315 (M+,
100), 108 (66). Anal. Calcd for C20H17N3O: C, 76.16; H, 5.44;
N, 13.33. Found: C, 76.02; H, 5.27; N, 13.15.
2-Azid o-2′-p h th a lim id obip h en yl. To a stirred solution of
2-amino-2′-phthalimidobiphenyl (6.3 g, 20 mmol) in 74 mL of
2 N HCl cooled at 0 °C was added dropwise a solution of
NaNO2 (1.66 g, 24 mmol) in 30 mL of water. The reaction
mixture was stirred at 0 °C for 45 min, and then a solution of
NaN3 (2.75 g, 42 mmol) in 40 mL of water was added. The
reaction mixture was allowed to warm at room temperature
for 5 h. The precipitated solid was collected by filtration, air-
dried, and chromatographed (silica gel, n-hexane/ethyl acetate
1:1) to give 2-a zid o-2′-p h th a lim id obip h en yl in 93% yield:
mp 154-156 °C; white prisms (dichloromethane); IR (Nujol)
2135, 1717 cm-1; 1H NMR (CDCl3) δ 7.03-7.82 (m); 13C NMR
(CDCl3) δ 118.7, 123.6, 124.7, 129.0, 129.1, 129.2, 130.2, 130.4,
131.0, 131.6, 131.7, 134.2, 137.3, 137.6, 167.1; mass spectrum
m/z (relative intensity) 315 (M+, 100). Anal. Calcd for
colorless prisms (n-hexane); IR (Nujol) 1670 cm-1 1H NMR
;
(CDCl3) δ 3.75 (s, 3H), 3.80 (s, 3H), 6.31-6.38 (m, 1H), 6.79-
7.46 (m, 14H), 7.94-8.02 (m, 1H); 13C NMR (CDCl3) δ 55.4,
55.5, 114.2, 114.6, 117.5, 120.2, 124.6, 124.9, 125.6, 127.5,
128.3, 128.8, 128.9, 131.2, 131.5, 132.6, 137.0, 141.4, 142.4,
143.8, 151.5, 156.7, 157.1, one quaternary carbon atom was
not observed; mass spectrum m/z (relative intensity) 446 (M+,
25), 254 (100). Anal. Calcd for C28H22N4O2: C, 75.32; H, 4.97;
N, 12.55. Found: C, 75.16; H, 5.08; N, 12.73.
1-(1-Na p h th yl)-2-(1-n a p h th yl)im in od iben zo[d ,f]-1,3-d i-
a zetid in o[1,2-a ]d ia zep in e (2d ): silica gel, n-hexane/dichlo-
romethane 7:3; 20% yield; mp 172-173 °C; colorless prisms
(diethyl ether); IR (Nujol) 1690 cm-1; 1H NMR (CDCl3) δ 6.57-
7.72 (m, 20H), 8.15-8.29 (m, 2H); 13C NMR (CDCl3) δ 116.4,
116.9, 123.5, 123.9, 124.6, 124.9, 125.2, 125.8, 126.0, 126.1,
126.5, 126.6, 127.7, 128.0, 128.7, 129.0, 129.1, 129.3, 129.5,
131.6, 131.6, 131.7, 132.8, 134.0, 134.1, 139.8, 142.6, 143.6,
144.0, 152.3, three methine carbon atoms and two quaternary
carbon atoms were not observed; mass spectrum m/z (relative
intensity) 486 (M+, 19), 294 (100). Anal. Calcd for C34H22N4:
C, 83.93; H, 4.56; N, 11.51. Found: C, 83.78; H, 4.43; N, 11,-
78.
1-[4-(Dim et h yla m in o)p h en yl]-2-[4-(d im et h yla m in o)-
p h e n yl]im in od ib e n zo[d ,f]-1,3-d ia ze t id in o[1,2-a ]d ia z-
ep in e (2e): silica gel, dichloromethane; 64% yield; mp 121-
123 °C dec; pale yellow prisms (chloroform/n-hexane); IR
(Nujol) 1687, 1677 cm-1; 1H NMR (CDCl3) δ 2.88 (s, 6H), 2.93
(s, 6H), 6.35-6.49 (m, 1H), 6.63 (d, 2H, J ) 8.7 Hz), 6.71-
6.77 (m, 2H), 7.00-7.45 (m, 9H), 7.82-7.97 (m, 2H); 13C NMR
C
20H12N4O2: C, 70.58; H, 3.55; N, 16.46. Found: C, 70.64; H,
3.21; N, 16.55.