N-Phosphino- and N-Phosphonionitrilimines
J . Org. Chem., Vol. 62, No. 2, 1997 295
Nitr ilim in e 2b. A CH2Cl2 solution (5 mL) of triphenylcar-
benium hexafluorophosphate (0.19 g, 0.48 mmol) was added
to a dichloromethane solution (10 mL) of N-phosphinonitril-
imine 1 (0.26 g, 0.48 mmol) at -78 °C. After 30 min at low
temperature, the mixture was allowed to warm to rt, 31P NMR
spectroscopy indicating the quantitative formation of N-
phosphonionitrilimine 2b. Evaporation of the solvent led to
the isolation of 2b as a spectroscopically pure yellow oil (0.38
g, 85% yield): 1H NMR (200 MHz, CDCl3) δ 1.33 (d, 24 H, J HH
) 6.9 Hz), 1.36 (d, 24 H, J HH ) 6.9 Hz), 3.85 (m, 8 H), 7.06-
7.29 (m, 15 H); 13C NMR (50 MHz, CDCl3) δ 22.3, 22.9, 23.7,
23.8, 47.1 (d, J PC ) 5.6 Hz), 48.6 (d, J PC ) 3.0 Hz), 68.1 (d, J PC
) 100.1 Hz), 69.2 (dd, J PC ) 103.2 and 10.1 Hz), 127.8, 128.3,
130.2 (d, J PC ) 3.7 Hz), 132.1 (d, J PC ) 13.6 Hz); 31P NMR (32
described above for compound 4) gave, after purification by
column chromatography with hexane as eluent, the thiadi-
azaphosphinine 11 as a brown solid (1.37 g, 75% yield): mp
85-86 °C dec; 1H NMR (300 MHz, CDCl3) δ 1.15 (d, 6 H, J HH
) 6.9 Hz), 1.21 (d, 6 H, J HH ) 6.9 Hz), 1.26 (d, 6 H, J HH ) 7.0
Hz), 1.31 (m, 30 H), 3.72 (m, 4 H), 3.94 (m, 4 H); 13C NMR (75
MHz, CDCl3) δ 22.5-24.0, 47.4 (d, J PC ) 5.5 Hz), 47.5 (d,
J PC ) 5.5 Hz), 141.1 (dd, J PC ) 158.6 Hz, J PC ) 49.4 Hz),
214 (dd, J PC ) 73.0 Hz, J PC ) 9.3 Hz); 31P NMR (150 MHz,
CDCl3) δ 3.6, 61.3; MS (El) m/z 610 (M+). Anal. Calcd for
C26H56N6P2S3: C, 51.12; H, 9.24; N, 13.76. Found: C, 51.10;
H, 9.14; N, 13.74.
[4,5-(4-Cyclop en ta n e-1,3-ylen e)[3-[Bis(d iisop r op yla m i-
n o)t h ioxop h osp h or a n yl]-2-p yr a zolin yl]b is(d iisop r op y-
la m in o)m eth ylp h osp h on iu m Tr ifla te (12). Reaction of 2,5-
norbornadiene (1.66 g, 18 mmol) with nitrilimine 2a (2.09 g,
3 mmol) for 48 h (as described above for compound 4) gave,
after recrystallization from THF/Et2O, the cycloadduct 12 (1.90
g, 80% yield): mp 147-148 °C dec; 1H NMR (300 MHz, CDCl3)
δ 1.34 (m, 48 H), 1.45 (d, 1 H, J HH ) 9.6 Hz), 1.66 (d, 1 H, J HH
) 9.6 Hz), 2.34 (d, 3 H, J PH ) 13.9 Hz), 3.14 (sbroad, 1 H), 3.80
(m, 9 H), 4.04 (sbroad, 1 H), 4.27 (d, 1 H, J HH ) 9.2 Hz), 6.10
(dd, 1 H, J HH ) 5.7 Hz, J HH ) 3.1 Hz), 6.29 (dd, 1 H, J HH ) 5.7
MHz, CDCl3) δ -144.9 (sept, J PF ) 712.1 Hz), 29.6 (d, J PP
)
5.7 Hz), 42.6 (d, J PP ) 5.7 Hz); IR (CH2Cl2) 2168 cm-1. Anal.
Calcd for C44H71N6F6P3S: C, 57.25; H, 7.75; N, 9.10. Found:
C, 57.30; H, 7.79; N, 9.15.
2,4-Bis[bis(d iisop r op yla m in o)th ioxop h osp h or a n yl]-7-
p h en yl-2,3,7-tr ia za bicyclo[3.3.0.]octa n e (4). To a THF
solution (5 mL) of nitrilimine 1 (1.60 g, 3 mmol) was added a
THF solution (10 mL) of N-phenylmaleimide (0.52 g, 3 mmol).
The mixture was stirred for 6 h at rt, and then sulfur (0.11 g,
3.3 mmol) was added to the mixture. After the mixture was
stirred for 2 h at rt, the solvent was removed under vacuum
and the crude residue was purified by flash column chroma-
tography (silica gel) with hexane as eluent to give pyrazoline
4 as an oil, which was recrystallized from pentane as a white
Hz, J HH ) 3.1 Hz); 13C NMR (75 MHz, CDCl3) δ 16.0 (d, J PC
)
103.2 Hz), 22.4-24.3, 42.9, 47.6 (d, J PC ) 6.0 Hz), 48.2 (d, J PC
) 5.0 Hz), 48.4 (d, J PC ) 5.5 Hz), 48.6 (d, J PC ) 6.0 Hz), 50.5,
62.3 (dd, J PC ) 20.9 Hz, J PC ) 4.8 Hz), 68.8 (t, J PC ) 5.5 Hz),
77.0, 120.6 (d, J FC ) 320.8 Hz), 135.6, 140.8, 159.6 (dd, J PC
) 135.3 and 11.9 Hz); 31P NMR (150 MHz, CDCl3) δ 52.6,
57.1; MS (El) m/z 576 (M+ -CF3SO3 - C5H7). Anal. Calcd
for C34H67F3N6O3P2S2: C, 51.63; H, 8.54; N, 10.62. Found: C,
51.70; H, 8.51; N, 10.64.
1
solid (1.88 g, 85% yield): mp 136-137 °C dec; H NMR (300
MHz, CDCl3) δ 1.31-1.45 (m, 48H), 3.75 (m, 6H), 4.11 (m, 2H),
4.42 (d, 1 H, J HH ) 10.3 Hz), 6.05 (dd, 1 H, J HH ) 10.3 Hz, J PH
) 4.6 Hz), 7.26-7.42 (m, 5H); 13C NMR (75 MHz, CDCl3) δ
23.3-24.9, 47.9 (d, J PC ) 5.5 Hz), 48.1 (d, J PC ) 6.0 Hz), 48.3
(d, J PC ) 5.5 Hz), 49.0 (d, J PC ) 6.0 Hz), 54.5 (dd, J PC ) 19.9
Hz, J PC ) 2.3 Hz), 65.4 (dd, J PC ) 11.1 Hz, J PC ) 2.0 Hz),
126.0-131.9, 148.8 (dd, J PC ) 151.1 Hz, J PC ) 7.1 Hz), 170.4
(d, J PC ) 2.0 Hz), 173.4; 31P NMR (150 MHz, CDCl3) δ 56.8,
64.7; IR (KBr) 1733 cm-1; MS (El) m/z 739 (M+). Anal. Calcd
for C35H63N7O2P2S2: C, 56.81; H, 8.58; N, 13.25. Found: C,
56.89; H, 8.55; N, 13.28.
[[3-[Bis(d iisop r op yla m in o)t h ioxop h osp h or a n yl]-4-
(et h oxyca r b on yl)-5-p yr r olid in yl]-2-p yr a zolin yl]b is(d i-
isop r op yla m in o)m eth ylp h osp h on iu m Tr ifla te (13). To a
THF solution (10 mL) of nitrilimine 2a (2.09 g, 3 mmol) was
added a toluene solution (15 mL) of ethyl trans-2-pyrrolidine-
acrylate (0.51 g, 3 mmol), and the mixture was stirred for 52
h at rt. Evaporation of the solvent under reduced pressure
afforded an oil which was recrystallized from Et2O to give 13
as a white solid (2.03 g, 78% yield): mp 89-90 °C dec; 1H NMR
(300 MHz, CDCl3) δ 1.27 (m, 51 H), 1.75 (m, 2 H), 1.82 (m, 2
H), 2.27 (d, 3 H, J PH ) 14.2 Hz), 2.54 (m, 4 H), 3.77 (m, 8 H),
4.14 (q, 2 H, J HH ) 7.2 Hz), 4.42 (t, 1 H, J HH ) J PH ) 2.9 Hz),
5.10 (t, 1 H, J HH ) J PH ) 2.9 Hz); 13C NMR (75 MHz, CDCl3)
δ 15.9 (d, J PC ) 99.7 Hz), 18.4, 23.3, 23.4-24.1, 46.7, 47.7 (d,
J PC ) 5.5 Hz), 47.8 (d, J PC ) 6.0 Hz), 48.6 (d, J PC ) 5.5 Hz),
49.0 (d, J PC ) 5.5 Hz), 55.1 (dd, J PC ) 19.6 and 5.0 Hz), 62.4,
80.6 (dd, J PC ) 7.4 and 3.4 Hz), 120.6 (d, J FC ) 319.8 Hz),
157.9 (dd, J PC ) 135.8 and 9.9 Hz), 170.3; 31P NMR (150 MHz,
CDCl3) δ 52.0, 56.4; IR (KBr) 1731, 1260 cm-1. Anal. Calcd
for C36H74F3N7O5P2S2: C, 49.81; H, 8.59; N, 11.29. Found: C,
49.89; H, 8.57; N, 11.33.
1,3-Bis[bis(d iisop r op yla m in o)th ioxop h osp h or a n yl]-5-
a cetylp yr a zolin e (6). Reaction of methyl vinyl ketone (0.21
g, 3 mmol) with nitrilimine 1 (1.60 g, 3 mmol) for 3 h and
addition of sulfur (0.11 g, 3.3 mmol) (as described above for
compound 4) gave, after purification by column chromatogra-
phy with hexane as eluent, the pyrazoline 6 as a white solid
(1.56 g, 82% yield): mp 84-85 °C dec; 1H NMR (300 MHz,
CDCl3) δ 1.19-1.36 (m, 48 H), 2.23 (s, 3H), 2.77-2.83 (m, 2
H), 3.59-4.17 (m, 8 H), 4.89 (m, 1 H); 13C NMR (150 MHz,
CDCl3) δ 22.7-24.3, 28.0, 40.4 (dd, J PC ) 24.7 Hz, J PC ) 5.0
Hz), 47.3 (d, J PC ) 5.5 Hz), 47.4 (d, J PC ) 6.0 Hz), 47.8 (d, J PC
) 5.5 Hz), 47.9 (d, J PC ) 6.0 Hz), 65.3 (dd, J PC ) 11.6 Hz, J PC
) 3.5 Hz), 149.5 (dd, J PC ) 149.3 Hz, J PC ) 8.8 Hz), 205.8; 31
P
NMR (150 MHz, CDCl3) δ 58.5 (d, J PP ) 3.8 Hz), 62.7 (d, J PP
) 3.8 Hz); IR (KBr) 1735, 1276 cm-1; MS (El) m/z 636 (M+).
Anal. Calcd for C29H62N6OP2S2: C, 54.69; H, 9.81; N, 13.19.
Found: C, 54.79; H, 9.80; N, 13.23.
[3-[Bis(d iisop r op yla m in o)t h ioxop h osp h or a n yl]-4-
(e t h o x y c a r b o n y l)p y r a zo ly l]b is (d iis o p r o p y la m in o )-
m eth ylp h osp h on iu m Tr ifla te (14). A toluene solution (15
mL) of pyrazoline 13 (1.73 g, 2 mmol) was heated at 50 °C for
15 h. Evaporation of solvent under reduced pressure afforded
an oil which was recrystallized from THF/Et2O to give 14 as
a white solid (1.19 g, 75% yield): mp 210-211 °C dec; 1H NMR
(300 MHz, CDCl3) δ 1.24 (m, 15 H), 1.29 (d, 12 H, J HH ) 7.0
Hz), 1.34 (d, 12 H, J HH ) 6.9 Hz), 1.39 (d, 12 H, J HH ) 6.7 Hz),
2.88 (d, 3 H, J PH ) 14.2 Hz), 3.84-4.02 (m, 8 H), 4.34 (q, 2 H,
J HH ) 7.2 Hz), 8.89 (sbroad, 1 H); 13C NMR (75 MHz, CDCl3)
3-[Bis(d iisop r op yla m in o)t h ioxop h osp h or a n yl]n a p h -
th oqu in oyl[2,3-d ]p yr a zole (8). Reaction of 1,4-naphtho-
quinone (0.47 g, 3 mmol) with nitrilimine 1 (1.60 g, 3 mmol)
for 2 h (as described above for compound 4) gave, after
purification by column chromatography with Et2O/hexane (1:
5) as eluent, the pyrazole 8 as a green solid (1.01 g, 73%
yield): mp 230-231 °C dec; 1H NMR (300 MHz, CDCl3) δ 1.18
(d, 12 H, J HH ) 6.9 Hz), 1.36 (d, 12 H, J HH ) 6.9 Hz), 1.44 (s,
1 H), 4.05 (m, 4 H), 7.71-8.29 (m, 4 H); 13C NMR (75 MHz,
CDCl3) δ 23.5-24.0, 48.1 (d, J PC ) 6.5 Hz), 120.4 (d, J PC ) 7.6
Hz), 124.5 (d, J PC ) 4.5 Hz), 127.2, 127.6, 133.6, 133.7, 134.2,
135.0, 141.7 (d, J PC ) 119.4 Hz), 179.1, 179.2; 31P NMR (150
MHz, CDCl3) δ 54.6; IR (KBr) 3282, 1680 cm-1; MS (El) m/z
460 (M+). Anal. Calcd for C23H33N4O2PS: C, 59.98; H, 7.22;
N, 12.16. Found: C, 59.94; H, 7.20; N, 12.14.
δ 14.1, 16.5 (d, J PC ) 102.2 Hz), 22.2-24.1, 47.9 (d, J PC
)
6.0 Hz), 49.7 (d, J PC ) 5.0 Hz), 65.8, 120.7 (d, J FC ) 320.8
Hz), 122.9, 141.3, 157.9 (dd, J PC ) 136.7 and 8.8 Hz), 161.1;
31P NMR (150 MHz, CDCl3) δ 49.7, 59.9; IR (KBr) 1743,
1273 cm-1; MS (El) m/z 647 (M+ - CF3SO3). Anal. Calcd for
C32H65F3N6O5P2S2: C, 48.23; H, 8.22; N, 10.54. Found: C,
48.18; H, 8.20; N, 10.57.
Clea va ge of Nitr ilim in e 1. A 1 M ether solution of HCl
(0.48 mL, 0.48 mmol) was added, at -78 °C, to a CH2Cl2
solution (10 mL) of N-phosphinonitrilimine 1 (0.26 g, 0.48
mmol). After 30 min at low temperature, the solution was
allowed to warm to rt, and 31P NMR spectroscopy indicated
2-[Bis(d iisop r op yla m in o)th ioxop h osp h or a n yl]-5,5-bis-
(d iisop r op yla m in o)-6-t h ioxo-1,6-d ih yd r o-1,3,4,5-t h ia d i-
a za p h osp h in in e (11). Reaction of carbon disulfide (0.23 g,
3 mmol) with nitrilimine 1 (1.60 g, 3 mmol) for 4 h (as