Synthesis, spectroscopic studies, and x-ray crystal structure of N-heteryliminophosphoranes

Article abstract of DOI:10.1080/10426500490262513

N-[2-(α-Bromoacetyl)phenyl]imides (prepared in two steps from 2-aminoacetophenone) gave, upon treatment with sodium azide, fused azidoquinolines via an intramolecular cyclization. Reaction of the above azides with phosphines gave N-heteryliminophosphoranes. The IR, ¹H-, ¹³C-, and ³¹P-NMR and MS spectra of these compounds as well as the x-ray crystal structure of two of them is reported.

Full text of DOI:10.1080/10426500490262513

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Phosphorus, Sulfur, and Silicon and the Related
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SYNTHESIS, SPECTROSCOPIC STUDIES,
AND X-RAY CRYSTAL STRUCTURE OF N-
HETERYLIMINOPHOSPHORANES
H. Z. Alkhathlan a , M. A. Al-Jaradah a , K. A. Al-Farhan a & A. A. Mousa a
a King Saud University , Riyadh, Saudi Arabia
Published online: 11 Aug 2010.
To cite this article: H. Z. Alkhathlan , M. A. Al-Jaradah , K. A. Al-Farhan & A. A. Mousa (2004) SYNTHESIS, SPECTROSCOPIC
STUDIES, AND X-RAY CRYSTAL STRUCTURE OF N-HETERYLIMINOPHOSPHORANES, Phosphorus, Sulfur, and Silicon and the Related
Elements, 179:2, 373-388, DOI: 10.1080/10426500490262513
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Phosphorus, Sulfur, and Silicon, 179:373–388, 2004
ꢀC
Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500490262513
SYNTHESIS, SPECTROSCOPIC STUDIES,
AND X-RAY CRYSTAL STRUCTURE OF
N-HETERYLIMINOPHOSPHORANES
H. Z. Alkhathlan, M. A. Al-Jaradah, K. A. Al-Farhan,
and A. A. Mousa
King Saud University, Riyadh, Saudi Arabia
(Received February 19, 2003; accepted August 12, 2003)
N-[2-(α-Bromoacetyl)phenyl]imides (prepared in two steps from 2-
aminoacetophenone) gave, upon treatment with sodium azide, fused
azidoquinolines via an intramolecular cyclization. Reaction of the
above azides with phosphines gave N-heteryliminophosphoranes. The
IR, 1H-, 13C-, and 31P-NMR and MS spectra of these compounds as well
as the x-ray crystal structure of two of them is reported.
Keywords: 2-Aminoacetophenone; acid anhydrides; azides; iminophos-
phoranes; quinoline
Iminophosphoranes (phosphine imines) have been known for almost
a century. They have been mostly prepared by either of two meth-
ods, reaction of phosphines with azides (Staudinger reaction) or reac-
tion of primary amines with phosphine dihalides in the presence of a
suitable base. The first method is the easiest and the most commonly
used method for the preparation of these types of compounds. Nowa-
days, the most important application of iminophosphoranes is their
use in the synthesis of nitrogen heterocyclic compounds via the inter-
and intramolecular aza-Wittig reactions. A large number of nitrogen-
containing heterocycles have been prepared using these reactions.1−8
We have previously reported the use of iminophosphoranes via the
aza- and bis-aza-Wittig reactions for the synthesis of heterocyclic sys-
tems such as imidazole, benzimidazole, perimidine, isoindole, and other
systems.9−11
In the majority of the previous reports, iminophosphoranes were not
isolated but rather used as intermediates in the aza-Wittig reactions.
Address correspondence to H. Z. Alkhathlan, Department of Chemistry, College of
Science, King Saud University P.O. Box 2455, Riyadh 11451, Saudi Arabia. E-mail:
khathlan@ksu.edu.sa
373

374
H. Z. Alkhathlan et al.
One of the difficulties in isolating them is that they are very susceptible
to hydrolysis to give the corresponding amines and phosphine oxides.
The cases were they have been isolated and fully characterized are
scattered throughout the literature.8,12−20
In a previous work we observed that N-heteryliminophosphoranes
were stable to a degree that they did not hydrolyze or react under
the aza-Wittig conditions.21 Herein we report some further investiga-
tion on the synthesis and x-ray crystal structure of new derivatives of
N-heteryliminophosphoranes.
RESULTS AND DISCUSSION
The imides 3a–d were readily prepared by condensation of 2-
aminoacetophenone with acid anhydrides (Scheme 1). In cases 2b
and 2d where 3-nitro- and 3,4,5,6-tetrachlorophthalic anhydrides were
used, the fused quinoline derivatives 4b and 4d were obtained along
with 3b and 3d respectively. Percentages of 4b and 4d were depen-
dent on the concentration of the base and reaction temperature. In-
creasing these two factors increases the percentages of 4b and 4d.
Bromination of 3a–d with copper bromide gave 5a–d. These compounds
showed in their 1H-NMR spectra signals at about δ 4.50 ppm for
the methylene group. Cyclization of 5a–d with sodium azide gave the
6-azidoisoindolo[2,1-a]quinoline ring system 6a–d. As it has been ob-
served by Alkhathlan and Al-Farhan21 and others,22 reaction of the
bromo derivatives 5a–d with sodium azide did not give substitution
products that would be the azido analogs of 5a–d but gave instead
the cyclized products 6a–d. Although our attempts to isolate the azido
analogs of 5a–d by running the reaction at room temperature failed, it
seems to be reasonable to assume that the conversion of 5a–d to 6a–d
proceeds in a substitution step first followed by cyclization.
Structures of 6a–d were confirmed by their IR, NMR, and MS spec-
tra. Their IR spectra showed an absorbance for the azido group at about
2120 cm−1, while the two carbonyl groups appeared as two absorption
bands at about 1745 and 1620 cm−1. Their 1H- and 13C-NMR spectra did
not show any aliphatic signals. The position carrying the azido group
(C6) appeared in the 13C-NMR at about δ 117 ppm. The MS spectra of
the azido derivatives 6a–d showed very weak molecular ions. They tend
to lose N2 very easily to give fragments at (M+-28) with high intensi-
ties. Other main fragmentation pathways are loss of 2CO and the NO2
group in 6b and 6c.
A point worth mentioning here is that although the cyclization of 5b
and 5c could give two products depending on the position of the nitro

Iminophosphoranes
375
SCHEME 1
group in the cyclized products (5b could give 6b and another product
were the NO2 group is in position 7 while 5c could give 6c and another
product were the NO2 group is in position 8), only 6b and 6c were
obtained. Their structures were confirmed based upon the structures
of their iminophosphorane derivatives 14 and 18 respectively.

376
H. Z. Alkhathlan et al.
TABLE I Iminophosphorane Derivatives 7–21
R1
R2
R3
R4
R5
Compound
H
H
H
H
H
Cl
H
H
H
Cl
H
H
H
H
H
H
H
H
H
H
Cl
H
H
H
Cl
H
H
H
H
H
H
NO2
H
H
NO2
Cl
H
H
NO2
Cl
H
NO2
H
H
NO2
H
Cl
H
NO2
H
Cl
NO2
H
Phenyl
Phenyl
p-Tolyl
p-Tolyl
p-Tolyl
p-Tolyl
Benzyl
Benzyl
Benzyl
Benzyl
Cyclohexyl
Cyclohexyl
Butyl
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
NO2
H
NO2
H
NO2
H
NO2
Butyl
Methoxy
Treatment of the azides 6a–d with a variety of phosphines (Table I)
resulted in the formation of the iminophosphoranes 7–21 in very good
yields. Structures of these compounds were confirmed by their IR,1H-,
13C-, and 31P-NMR, MS, and x-ray crystallography. The IR spectra of
7–21 showed absorbances for the C5 and C11 carbonyl groups at about
1
1620 and 1720 cm−1 respectively. The H-NMR spectra of compounds
13–16 showed signals for the benzylic CH2 groups in the range δ 3.40-
3.57 ppm as doublets with J = 13.50–14.28 Hz as a result of the coupling
with the phosphorous nuclei. This coupling was not as clear in com-
pounds 17–20, the signals appeared as multiplets because of coupling
with other adjacent protons. A three-bond coupling could be observed
between the phosphorous nuclei and protons of the methoxy group in
21. The signal for the methoxy group in the latter compound appeared
as doublet with J = 11.72 Hz.
The 13C-NMR spectra of compounds 7–21 showed signals for the two
carbonyl groups in the range δ 160–180 ppm, the heterocyclic ring sys-
tem between δ 117–146 ppm and the R5 groups depending on its nature.
The signal for the ketonic carbonyl group at C5 in all the above com-
pounds was split by the phosphorous nuclei via a three-bond coupling
with J = 33–42 Hz. The C1 of the R5 group attached to the phosphorous
was also split to doublet with coupling constants varying depending on
whether it has an aliphatic or aromatic character. As was the case in
1H-NMR, the 13C-NMR spectrum of compound 21 showed the signal for
the methoxy group split into a doublet with J = 27.56 Hz. Table II shows
the IR absorbances for the N P and 13C-NMR chemical shifts and cou-
pling constants for the C1 of the R5 group attached to the phosphorous

Iminophosphoranes
377
TABLE II Selected IR, 13C- and 31P-NMR Data for Compounds 7–21
13C-NMR (J, Hz)
Compound
IR N
1438
P
P
C
C5
31P-NMR
7
8
9
128.50 (48.92)
128.54 (48.96)
128.77 (52.00)
129.08 (52.00)
129.14 (52.01)
129.11 (59.02)
35.22 (241.60)
36.47 (241.61)
36.52 (241.64)
35.38 (238.56)
39.16 (235.52)
39.16 (232.44)
28.47 (256.92)
29.62 (256.95)
55.13 (27.56) (P
177.38 (33.64)
177.32 (36.72)
173.10 (42.84)
177.31 (33.64)
177.28 (33.64)
180.27 (33.74)
174.52 (39.50)
179.45 (36.68)
179.34 (36.68)
179.25 (36.86)
178.75 (33.64)
175.72 (33.69)
179.25 (33.64)
179.63 (33.63)
177.90 (33.64)
19.34
19.79
22.72
19.16
19.66
15.26
31.81
26.19
23.62
23.62
36.39
37.14
32.64
32.67
9.71
1436
1440
1445
1435
1457
1435
1446
1420
1453
1445
1439
1443
1435
1466
10
11
12
13
14
15
16
17
18
19
20
21
O
C)
(P C) and the ketonic carbonyl group (C5) in addition to the 31P-NMR
signals for compounds 7–21. The rest of the spectroscopic data is shown
in the experimental section.
The MS spectra of the iminophosphoranes 7–21 showed molecular
ions agreeing with the expected molecular weights. Compounds origi-
nating from the acid anhydrides 2b and 2c (i.e., 7, 8, 10, 11) have very
stable molecular ions which in some cases represent the base peak. The
main fragmentation pathways are the consequent loss of the three R5
groups or the complete loss of the iminophosphorane moiety.
Structures of the iminophosphoranes 14 and 18 are confirmed using
x-ray crystallography. Figures 1 and 2 show the crystal structures of 14
and 18 respectively. Relevant crystallographic data are summarized in
Table III while selected geometrical parameters are given in Table IV.
EXPERIMENTAL
Melting points are uncorrected. IR spectra were recorded on a Perkin-
Elmer 883 spectrophotometer as KBr pellets and expressed as ν in cm−1
.
NMR spectra were recorded on JEOL ECP 400 (400 MHz) in CDCl3 and
chemical shifts are expressed as δ in ppm. MS spectra were recorded
on Shimadzu QP 5050A GC/MS system. Microanalysis was performed
at KACST Research Laboratories.

378
H. Z. Alkhathlan et al.
FIGURE 1 X-ray crystal structure of 14.
FIGURE 2 X-ray crystal structure of 18.

Iminophosphoranes
379
TABLE III Crystal Data, Intensity Data Collection Parameters, and
Structure Refinement Results for 14 and 18
18
14
Crystal data
Chemical formula
Formula weight
Colour of crystal
Size of specimen (mm)
Crystal system
Space group
C34H40N3O4P
585.66
Red
C37H28N3O4P
609.59
Red
0.20 × 0.20 × 0.10
Monoclinic
P21/c
18.716(1)
10.869(1)
16.059(1)
114.320(6)
2976.9(4)
4
0.36 × 0.24 × 0.22
Monoclinic
P21/c
10.9239(1)
16.3707(3)
17.2625(3)
99.094(1)
3048.28(8)
4
˚
a (A)
˚
b (A)
˚
c (A)
β (o)
V (A )
3
˚
Z
Dcalc. (g cm−3
)
1.307
0.255
1248
1.328
0.137
1272
µ (Mo-Kα) (mm−1
F(000)
)
Data collection
Diffractometer
Radiation, λ (A)
Siemens P4
Mo-Kα, 0.71073
Graphite
Siemens SMART CCD
Mo-Kα, 0.71073
Graphite
˚
Monochromator
Range of h, k, l
−20 ≤ h ≥ 18, −11 ≤ k ≥ 1,
−12 ≤ h ≥ 12, −19 ≤ k ≥ 15,
−1 ≤ l ≥ 17
−18 ≤ l ≥ 20
No. of independent
reflections
4855
5338
Rint
0.0427
2083
0.1507
3008
No. of observed
reflections
Cut-off criteria
Absorption corrections
Structure refinement
Refinement on
R[F > 4σ(F)]
wR (F2)
Fo > 4σ(Fo)
Non
Fo > 4σ(Fo)
Non
F2
0.0524
0.0981
F2
0.0617
0.1252
w
1/[σ2(F02) + (0.0524P)2
1/[σ2(F02) + (0.0003P)2
+ 0.0P]
+ 0.0P]
where P = (F02 + 2F2)/3
where P = (F02 + 2F2)/3
c
c
S
0.998
4440
0.861
5325
No. of independent
reflections
No. of parameters
refined
380
407
−3
˚
ꢀρ (e A
)
0.189, −0.254
0.416, −0.637

380
H. Z. Alkhathlan et al.
˚
TABLE IV Selected Geometrical Parameters. Lengths (A)
and Angles (◦) for 14 and 18
18
14
Bond lengths
P(1) C(23)
P(1) C(29)
1.831 (4)
1.829 (4)
P(1) C(24)
P(1) C(31)
P(1) C(17)
P(1) N(3)
N(3) C(9)
C(10) O(1)
C(7) O(2)
N(2) O(3)
1.825 (3)
1.838 (3)
1.847 (3)
1.593 (2)
1.375 (3)
1.243 (3)
1.212 (3)
1.234 (4)
1.217 (4)
1.846 (4)
1.586 (3)
1.346 (5)
1.241 (4)
1.209 (5)
1.223 (5)
1.223 (5)
1.471 (5)
N(2) O(4)
N(2) C(2)
N(2) C(1)
C(9) C(8)
C(8) C(5)
C(5) C(6)
C(6) C(7)
N(1) C(7)
N(1) C(8)
N(1) C(16)
1.471 (4)
1.389 (3)
1.458 (3)
1.402 (4)
1.497 (4)
1.424 (3)
1.417 (3)
1.411 (3)
1.411 (4)
1.481 (4)
1.491 (4)
1.382 (5)
1.441 (6)
1.401 (5)
1.468 (6)
1.429 (5)
1.408 (5)
1.396 (5)
1.400 (5)
1.464 (6)
1.464 (6)
C(16) C(11)
C(11) C(10)
C(10) C(9)
Bond angles
N(3) P(1) C(17)
N(3) P(1) C(23)
N(3) P(1) C(29)
P(1) N(3) C(9)
N(3) C(9) C(8)
N(3) C(9) C(10)
C(8) C(9) C(10)
O(1) C(10) C(9)
O(1) C(10) C(11)
C(9) C(10) C(11)
O(2) C(7) N(1)
O(2) C(7) C(6)
N(1) C(7) C(6)
O(3) N(2) O(4)
Torsion angles
C(17) P(1) N(3) C(9)
C(23) P(1) N(3) C(9)
C(29) P(1) N(3) C(9)
C(24) P(1) N(3) C(9)
C(31) P(1) N(3) C(9)
114.2 (2)
103.3 (2)
119.3 (2)
133.5 (3)
120.8 (4)
123.5 (4)
115.7 (4)
119.6 (4)
122.0 (4)
118.4 (4)
125.9 (4)
129.6 (4)
104.6 (4)
123.2 (4)
114.7 (1)
104.6 (1)
119.6 (1)
131.8 (2)
119.7 (2)
123.6 (2)
116.7 (3)
119.7 (3)
121.7 (3)
118.6 (2)
126.1 (3)
129.1 (3)
104.8 (2)
124.4 (3)
−75.4 (4)
171.5 (4)
52.9 (5)
66.5 (3)
175.8 (2)
62.3 (3)
175.8 (2)
62.3 (3)

Iminophosphoranes
381
N-(2-Acetylphenyl)phthalimide, 3a: A solution of 10.0 g (74.0 mmol)
of 2-aminoacetophene (1), 13.1 g (88.5 mmol) of phthalic anhydride (2a)
and 2 mL of triethylamine in 350 mL of xylene was refluxed for 5 h.
The resulting solid was collected and recrystallized from ethanol. Yield,
90%, colorless solid, m.p. 134◦C (136◦C).23
N-(2-Acetylphenyl)-3-nitrophthalimide, 3b; 10-Nitro-5H,11H-isoindolo
[2,1-a]quinoline-5,11-dione, 4b: These two compounds were obtained
from (1) and 3-nitrophthalic anhydride (2b) in a procedure similar to
that described for (3a). Compound (4b) was obtained from the filtrate
of (3b). 3b, 52% yield, pale yellow solid, m.p. 185◦C (184◦C).23 4b, 30%
yield, yellow solid, m.p. 231◦C (233◦C).23
N-(2-Acetylphenyl)-4-nitrophthalimide, 3c: This compound was ob-
tained from (1) and 4-nitrophthalic anhydride (2d) in a procedure sim-
ilar to that described for (3a). 93% yield, yellow solid, m.p. 139◦C; IR:
1
1784, 1719, 1620. H-NMR: 2.58 (s, 3H), 7.45–8.72 (m, 7H); MS: m/z
(%) 310 (M+, 23), 295 (100), 249 (48), 193 (10), 164 (10), 75 (25). Anal.
Calcd. for C16H10N2O5: C, 61.93; H, 3.22; N, 9.03. Found: C, 61.75; H,
3.28; N, 8.91.
N-(2-Acetylphenyl)-3,4,5,6-tetrachlorophthalimide, 3d; 7,8,9,10-
Tetrachloro-5H,11H-isoindolo[2,1-a]quinoline-5,11-dione, 4d: These
two compounds were obtained from (1) and 3,4,5,6-tetrachlorophthalic
anhydride (2d) in a procedure similar to that described for (3b) and
(4b). 3d, 88% yield, pale yellow solid, m.p. 219◦C; IR: 1785, 1715, 1685.
1H-NMR: 2.59 (s, 3H), 7.64–7.93 (m, 4H). MS: m/z (%) 407 (M+6, 3), 405
(M+4, 9.5), 403 (M+2, 21), 401 (M+, 16), 388 (100), 360 (22), 214 (12), 90
(16). Anal. Calcd. for C16H7Cl4NO3: C, 47.64; H, 1.73; N, 3.47. Found: C,
47.60; H, 1.69; N, 3.40. 4d, 8% yield, yellow solid, m.p. 316◦C; IR: 1733,
1633. 1H-NMR: 6.95 (s, 1H), 7.20–7.80 (m, 4H). MS: m/z (%) 389 (M+6
,
11), 387 (M+4, 48), 385 (M+2, 97), 383 (M+, 78), 357 (100), 292 (24), 178
(35), 111 (15), 91 (8). Anal. Calcd. for C16H5Cl4NO2: C, 49.87; H, 1.30;
N, 3.63. Found: C, 49.71; H, 1.26; N, 3.72.
N-[2-(α-Bromoacetyl)phenyl]phthalimide, 5a: A solution of 5.0 g
(22.3 mmol) of CuBr2 in 200 mL of ethyl acetate was heated to reflux
after which a solution of 3.0 g (11.3 mmol) of (3a) in 100 mL of chloro-
form was added. Reflux was continued for 5 h. The mixture was filtered
while hot and the filtrate washed with water (2 × 50 mL). The organic
layer was dried over anhydrous magnesium sulphate and then evapo-
rated to dryness. The resulting solid was recrystallized from ethanol.
82% yield, yellow solid, m.p. 190◦C (m.p. 194◦C).21
N-[2-(α-Bromoacetyl)phenyl]-3-nitrophthalimide, 5b: This compound
was obtained from (3b) and CuBr2 in a procedure similar to that de-
scribed for (5a). 90% yield, pale yellow solid, m.p. 191◦C; IR: 1785, 1708,
1615. 1H-NMR: 4.56 (s, 2H), 7.41–8.19 (m, 7H). MS: m/z (%) 390 (M+2
,

382
H. Z. Alkhathlan et al.
1), 388 (M+, 1), 295 (100), 248 (21), 193 (5), 90 (6), 75 (20). Anal. Calcd.
for C16H9BrN2O5: C, 49.38; H, 2.33; N, 7.19. Found: C, 49.27; H, 2.21;
N, 7.01.
N-[2-(α-Bromoacetyl)phenyl]-4-nitrophthalimide, 5c: This compound
was obtained from (3c) and CuBr2 in a procedure similar to that
described for (5a). 70% yield, colorless solid, m.p. 180◦C; IR: 1783, 1720,
1620. 1H-NMR: 4.49 (s, 2H), 7.44–8.18 (m, 7H). MS: m/z (%) 390 (M+2
,
1), 388 (M+, 1), 295 (100), 249 (37), 193 (8), 90 (3), 75 (21). Anal. Calcd.
for C16H9BrN2O5: C, 49.38; H, 2.33; N, 7.19. Found: C, 48.92; H, 2.25;
N, 7.25.
N-[2-(α-Bromoacetyl)phenyl]-3,4,5,6-tetrachlorophthalimide, 5d:
This compound was obtained from (3d) and CuBr2 in a procedure sim-
ilar to that described for (5a). 95% yield, yellow solid, m.p. 227◦C; IR:
1
1783, 1716, 1633. H-NMR: 4.49 (s, 2H), 7.46–7.92 (m, 4H). MS: m/z
(%) 481 (M+2, 1), 479 (M+, 1), 392 (12), 388 (100), 386 (76), 216 (6), 146
(7), 90 (13). Anal. Calcd. for C16H6BrCl4NO3: C, 39.83; H, 1.24; N, 2.90.
Found: C, 39.72; H, 1.17; N, 2.83.
6-Azido-5H,11H-isoindolo[2,1-a]quinoline-5,11-dione, 6a: To a solu-
tion of 2.0 g (5.8 mmol) of (5a) in 70 mL of acetone was added a so-
lution of 0.45 g (6.9 mmol) of NaN3 in 20 mL of water. The mixture
was heated at 65◦C for 2 h. The resulting solid was collected and re-
crystallized from ethanol. 76% yield, brownish solid, m.p. 126◦C (m.p.
126◦C).21
6-Azido-10-nitro-5H,11H-isoindolo[2,1-a]quinoline-5,11-dione, 6b:
This compound was obtained from (5b) and NaN3 in a procedure similar
to that described for (6a). 53% yield, brownish solid, m.p. 195◦C; IR:
2125, 1746, 1624. 1H-NMR: 7.42–7.88 (m, 4H), 8.20–8.70 (m, 2H), 9.13
(d, J = 8.2 Hz, 1H); 13C-NMR: 117.90, 119.52, 123.47, 125.34, 126.41,
126.82, 129.36, 130.29, 133.87, 134.64, 135.40, 136.75, 141.20, 146.96,
160.37, 176.95. MS: m/z (%) 333 (M+, 5), 305 (49), 293 (17), 275 (17),
231 (43), 203 (49), 176 (49), 146 (40), 90 (16), 75 (100). Anal. Calcd. for
C16H7N5O4: C, 57.65; H, 2.10; N, 21.02. Found: C, 57.84; H, 2.21; N,
21.22.
6-Azido-9-nitro-5H,11H-isoindolo[2,1-a]quinoline-5,11-dione, 6c:
This compound was obtained from (5c) and NaN3 in a procedure
similar to that described for (6a). 59% yield, brownish solid, m.p.
208◦C; IR: 2128, 1746, 1622. 1H-NMR: 7.14–7.75 (m, 4H), 8.23 (d,
J = 8.3 Hz, 1H), 9.05–9.15 (m, 2H); 13C-NMR: 116.18, 117.50, 123.10,
124.08, 124.82, 125.11, 127.90, 131.21, 133.01, 133.54, 133.62, 134.60,
139.52, 145.89, 160.75, 175.85. MS: m/z (%) 333 (M+, 8), 305 (88), 275
(22), 261 (46), 231 (79), 203 (89), 175 (35), 151 (56), 102 (34), 75 (100).
Anal. Calcd. for C16H7N5O4: C, 57.65; H, 2.10; N, 21.02. Found: C,
57.77; H, 2.16; N, 21.10.

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6-Azido-7,8,9,10-tetrachloro-5H,11H-isoindolo[2,1-a]quinoline-5,11-
dione, 6d: This compound was obtained from (5d) and NaN3 in a
procedure similar to that described for (6a). 42% yield, brownish
1
solid, m.p. 215◦C; IR: 2119, 1787, 1610. H-NMR: 7.05–7.90 (m, 4H);
13C-NMR: 116.88, 119.94, 120.74, 125.11, 127.64, 127.98, 129.87,
135.88, 136.27, 137.18, 137.92, 140.34, 160.14, 186.87. MS: m/z (%)
424 (M+, 5), 396 (82), 361 (100), 317 (78), 214 (39), 142 (19), 76 (41).
Anal. Calcd. for C16H4Cl4N4O2: C, 45.07; H, 0.93; N, 13.14. Found: C,
45.23; H, 1.02; N, 13.05.
General Procedure for the Synthesis
of Iminophosphoranes 7–21
A solution of the appropriate azide (1.5 mmol) and the appropriate phos-
phine (2.2 mmol) in 60 mL of dry THF was heated to reflux for 2 h. The
solvent was evaporated under vacuum and the resulting solid was re-
crystallized from ethanol or mixture of ethanol and chloroform.
N-[(10-Nitro-5H,11H-isoindolo [2,1-a]quinoline-5,11-dione)-6-yl]
iminotriphenylphosphorane, 7: This compound was obtained from
(6b) and Ph3P. 86% yield, red solid, m.p. 260◦C; IR: 1719, 1623,
1
1438. H-NMR: 7.18 (t, J = 8.1 Hz, 1H), 7.46-7.63 (m, 7H), 7.74–7.92
(m, 11H), 8.0 (d, J = 8.1 Hz, 1H), 9.09 (d, J = 7.9 Hz, 1H), 9.22
(d, J = 8.1 Hz, 1H). 13C-NMR: 118.04, 118.28, 121.98, 122.05,
124.72, 126.55, 127.37, 128.50 (d, J = 48.92 Hz), 128.91, 131.30,
132.14 (d, J = 39.76 Hz), 132.65, 133.71 (d, J = 18.36 Hz), 134.02,
136.57 (d, J = 21.40 Hz), 136.85, 138.95, 146.96, 160.32, 177.38 (d,
J = 33.64 Hz). MS: m/z (%) 567 (M+, 100), 539 (13), 304 (24), 277
(10), 262 (43), 201 (10), 183 (86), 108 (25), 77 (7). Anal. Calcd. for
C34H22N3O4P: C, 71.95; H, 3.92; N, 7.49. Found: C, 71.88; H, 3.81;
N, 7.35.
N-[(9-Nitro-5H,11H-isoindolo[2,1-a]quinoline-5,11-dione)-6-yl]-
iminotriphenylphosphorane, 8: This compound was obtained from
(6c) and Ph3P. 80% yield, red solid, m.p. 331◦C; IR: 1720, 1625, 1436.
1H-NMR: 7.12 (t, J = 7.8 Hz, 1H), 7.42–7.67 (m, 9H), 7.55 (t, J =
7.8 Hz, 1H), 7.72–7.83 (m, 6H), 7.89 (d, J = 8.4 Hz, 1H), 8.35 (d, J =
7.8 Hz, 1H), 8.68 (d, J = 1.6 Hz, 1H), 8.82 (d, J = 7.8 Hz, 1H), 9.15
(dd, J1 = 8.4 Hz, J2 = 1.6 Hz, 1H). 13C-NMR: 117.78, 117.91, 120.24,
121.94, 124.73, 125.16, 125.48, 127.51, 128.54 (d, J = 48.96 Hz), 128.66,
131.41, 132.51 (d, J = 36.68 Hz), 132.27, 133.38, 134.17, 137.14, 141.21,
146.88, 163.63, 177.32 (d, J = 36.72 Hz). MS: m/z (%) 567 (M+, 69), 539
(7), 490 (8), 399 (6), 288 (11), 277 (11), 262 (18), 233 (8), 183 (100), 133
(7), 108 (45), 77 (19). Anal. Calcd. for C34H22N3O4P: C, 71.95; H, 3.92;
N, 7.49. Found: C, 71.98; H, 3.96; N, 7.55.

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N-[(5H,11H-isoindolo[2,1-a]quinoline-5,11-dione)-6-yl]iminotri- p-
tolylphosphorane, 9: This compound was obtained from (6a) and
tri-p-tolylphosphine. 53% yield, orange solid, m.p. 241◦C; IR: 1719,
1621, 1440. 1H-NMR: 2.39 (s, 9H), 7.19–7.24 (m, 9H), 7.32 (t, J =
7.32 Hz, 1H), 7.45–7.90 (m, 8H), 7.63 (dd, J1 = 7.68 Hz, J2 = 1.46 Hz,
1H), 8.0 (dd, J1 = 7.68 Hz, J2 = 1.46 Hz, 1H). 13C-NMR: 20.96, 114.29,
115.21, 121.74, 122.70, 122.99, 123.72, 128.19, 128.77 (d, J = 52.00 Hz),
128.97, 129.90, 131.47, 131.92, 132.13, 132.24 (d, J = 42.80 Hz), 133.09,
135.51, 135.79, 165.98, 173.10 (d, J = 42.84 Hz). MS: m/z (%) 448 (M+-
116, 2), 419 (4), 346 (17), 319 (100), 267 (10), 229 (15), 182 (7), 91 (21),
76 (8). Anal. Calcd. for C37H29N2O2P: C, 78.72; H, 5.14; N, 4.96. Found:
C, 78.55; H, 5.05; N, 4.85.
N-[(10-Nitro-5H,11H-isoindolo[2,1-a]quinoline-5,11-dione)-6-yl]
iminotri-p-tolylphosphorane, 10: This compound was obtained from
(6b) and tri-p-tolylphosphine. 98% yield, red solid, m.p. 290◦C; IR:
1710, 1619, 1445. 1H-NMR: 2.38 (s, 9H), 7.20 (t, J = 7.9 Hz, 1H),
7.25–7.45 (m, 7H), 7.63–7.81 (m, 8H), 7.99 (t, J = 8.02 Hz, 1H), 9.14
(d, J = 8.02 Hz, 1H), 9.22 (d, J = 7.9 Hz, 1H). 13C-NMR: 21.51, 117.92,
118.05, 121.69, 122.06, 124.50, 126.48, 127.35, 128.81, 129.08 (d, J =
52.00 Hz), 129.49, 130.55, 132.02 (d, J = 39.76 Hz), 133.52, 133.79,
136.74, 138.89, 141.43 (d, J = 12.20 Hz), 146.83, 160.19, 177.31 (d,
J = 33.64 Hz). MS: m/z (%) 609 (M+, 100), 579 (23), 346 (16), 319
(11), 304 (81), 213 (120), 183 (14), 122 (25), 76 (14). Anal. Calcd. for
C37H28N3O4P: C, 72.89; H, 4.62; N, 6.89. Found: C, 72.52; H, 4.56;
N, 6.84.
N-[(9-Nitro-5H,11H-isoindolo[2,1-a]quinoline-5,11-dione)-6-yl]-
iminotri-p-tolylphosphorane, 11: This compound was obtained from
(6c) and tri-p-tolylphosphine. 83% yield, red solid, m.p. 306◦C; IR:
1
1717, 1625, 1435. H-NMR: 2.31 (s, 9H), 7.10–7.25 (m, 7H), 7.51–7.62
(m, 7H), 7.91 (t, J = 8.78 Hz, 1H), 8.32 (dd, J1 = 8.42 Hz, J2 = 1.83 Hz,
1H), 8.65 (d, J = 1.83 Hz, 1H), 8.83 (d, J = 8.78 Hz, 1H), 9.13 (d, J =
8.78 Hz, 1H). 13C-NMR: 21.54, 117.65, 117.78, 120.09, 121.96, 124.50,
125.34, 127.48, 128.19, 129.14 (d, J = 52.01 Hz), 129.23, 130.24,
132.08 (d, J = 42.84 Hz), 132.11, 133.72, 133.93, 141.12, 141.62 (d, J =
12.24 Hz), 146.61, 163.50, 177.28 (d, J = 33.64 Hz). MS: m/z (%) 609
(M+, 100), 518 (10), 346 (13), 319 (49), 304 (26), 265 (11), 213 (25), 183
(15), 122 (25), 75 (33). Anal. Calcd. for C37H28N3O4P: C, 72.89; H, 4.62;
N, 6.89. Found: C, 72.44; H, 4.71; N, 6.69.
N-[(7,8,9,10-Tetrachloro-5H,11H-isoindolo[2,1-a]quinoline-5,11-
dione)-6-yl]iminotri-p-tolylphosphorane, 12: This compound was
obtained from (6d) and tri-p-tolylphosphine. 78% yield, red solid, m.p.
291◦C; IR: 1716, 1623, 1457. 1H-NMR: 2.30 (s, 9H), 7.10–7.32 (m, 13H),
7.64 (t, J = 8.4 Hz, 1H), 7.88 (d, J = 8.4 Hz, 1H), 9.12 (d, J = 8.4 Hz,

Iminophosphoranes
385
1H). 13C-NMR: 21.65, 118.26, 121.43, 123.01, 124.95, 126.89, 127.75,
127.98, 129.11 (d, J = 59.02 Hz), 130.10, 130.36, 131.65, 132.40 (d, J =
40.73 Hz), 134.24, 135.52, 136.29, 137.15, 138.45, 141.05, 160.34,
180.27 (d, J = 33.74 Hz). MS: m/z (%) 702 (M+2, 6), 700 (M+, 6), 414
(11), 360 (23), 346 (100), 319 (20), 227 (14), 213 (19), 91 (15), 75 (12).
Anal. Calcd. for C37H25Cl4N2O2P: C, 63.24; H, 3.56; N, 3.98. Found: C,
63.42; H, 3.61; N, 3.81.
N-[(5H,11H-isoindolo[2,1-a]quinoline-5,11-dione)-6-yl]iminotri-
benzylphosphorane, 13: This compound was obtained from (6a) and
tribenzylphosphine. 67% yield, orange solid, m.p. 183◦C; IR: 1719,
1
1620, 1435. H-NMR: 3.57 (d, J = 14.28 Hz, 6H), 7.16–7.78 (m, 21H),
8.28 (dd, J1 = 8.05 Hz, J2 = 1.46 Hz, 1H), 9.25 (t, J = 8.42 Hz, 1H).
13C-NMR: 35.22 (d, J = 241.60 Hz), 115.25, 117.77, 118.50, 121.79,
122.36, 124.67, 126.52, 127.27, 128.88 (d, J = 9.20 Hz), 130.28 (d,
J = 21.40 Hz), 131.52, 131.92, 134.25, 135.17, 135.93, 137.24, 138.12,
163.29, 174.52 (d, J = 39.50 Hz). MS: m/z (%) 564 (M+, 2), 473 (2), 320
(2), 307 (100), 279 (3), 251 (7), 223 (5), 91 (77), 75 (12). Anal. Calcd. for
C37H29N2O2P: C, 78.72; H, 5.14; N, 4.96. Found: C, 78.48; H, 5.19; N,
4.89.
N-[(10-Nitro-5H,11H-isoindolo[2,1-a]quinoline-5,11-dione)-6-yl]-
iminotribenzylphosphorane, 14: This compound was obtained from
(6b) and tribenzylphosphine. 78% yield, red solid, m.p. 235◦C; IR:
1
1718, 1632, 1446. H-NMR: 3.47 (d, J = 13.56 Hz, 6H), 7.09–7.31 (m,
17H), 7.45 (t, J = 8.41 Hz, 1H), 7.62 (t, J = 8.41 Hz, 1H), 8.15 (dd, J1 =
8.05 Hz, J2 = 1.46 Hz, 1H), 8.25 (dd, J1 = 8.05 Hz, J2 = 1.46 Hz, 1H),
9.17 (d, J = 8.41 Hz, 1H). 13C-NMR: 36.47 (d, J = 241.61 Hz), 117.82,
118.07, 121.79, 122.51, 124.93, 126.99, 127.12, 128.63, 128.74 (d, J =
9.16 Hz), 129.87, 130.27 (d, J = 21.40 Hz), 132.65 (d, J = 27.52 Hz),
133.63, 134.25, 136.77, 137.09, 139.01, 146.70, 160.32, 179.45 (d, J =
36.68 Hz). MS: m/z (%) 609 (M+, 22), 579 (4), 518 (23), 488 (6), 336 (8),
306 (11), 262 (5), 91 (100), 77 (6). Anal. Calcd. for C37H28N3O4P: C,
72.89; H, 4.62; N, 6.89. Found: C, 72.56; H, 4.62; N, 6.90.
X-Ray Structure Determination for 14 and 18
Suitable crystals for single-crystal diffraction studies were prepared by
crystallization from ethanol. The structure was solved by direct meth-
ods using SHELXS24 and refined by full-matrix least squares method
using SHELXLT97.25 Each of the hydrogen atoms was included in
the refinement at calculated position with isotropic thermal parame-
ter equal to 1.2Ueq of the atom to which it is bonded.
N-[(9-Nitro-5H,11H-isoindolo[2,1-a]quinoline-5,11-dione)-6-yl]imino-
tribenzylphosphorane, 15: This compound was obtained from (6c)

386
H. Z. Alkhathlan et al.
and tribenzylphosphine. 94% yield, red solid, m.p. 211◦C; IR: 1716,
1
1617, 1420. H-NMR: 3.49 (d, J = 13.50 Hz, 6H), 7.08–7.29 (m, 15H),
7.32 (t, J = 8.04 Hz, 1H), 7.65 (t, J = 8.04 Hz, 1H), 7.89 (d, J =
7.90 Hz, 1H), 8.02 (dd, J1 = 7.90 Hz, J2 = 1.46 Hz, 1H), 8.28 (d, J =
8.04 Hz), 8.61 (d, J = 1.46 Hz, 1H), 9.20 (d, J = 8.04 Hz, 1H). 13C-NMR:
36.52 (d, J = 241.64 Hz), 117.92, 118.04, 120.01, 122.33, 125.00,
125.32, 127.08, 127.20, 127.38, 128.28, 128.91 (d, J = 6.12 Hz), 130.32
(d, J = 18.36 Hz), 132.55 (d, J = 27.56 Hz), 134.46, 136.92, 137.15,
141.00, 146.79, 163.72, 179.34 (d, J = 36.68 Hz). MS: m/z (%) 609 (M+,
15), 518 (41), 336 (20), 320 (10), 290 (18), 262 (4), 123 (5), 91 (100), 76
(7). Anal. Calcd. for C37H28N3O4P: C, 72.89; H, 4.62; N, 6.89. Found: C,
72.96; H, 4.51; N, 6.73.
N-[(7,8,9,10-Tetrachloro-5H,11H-isoindolo[2,1-a]quinoline-5,11-
dione)-6-yl]iminotribenzylphosphorane, 16: This compound was ob-
tained from (6d) and tribenzylphosphine. 60% yield, red solid, m.p.
237◦C; IR: 1716, 1620, 1453. 1H-NMR: 3.40 (d, J = 13.90 Hz, 6H),
7.05–7.27 (m, 15H), 7.30 (t, J = 8.42 Hz, 1H), 7.61 (t, J = 8.42 Hz, 1H),
8.27 (d, J = 8.42 Hz, 1H), 9.15 (d, J = 8.42 Hz, 1H). 13C-NMR: 35.38
(d, J = 238.56 Hz), 118.31, 121.63, 124.17, 124.81, 126.96, 127.02,
127.29, 128.68 (d, J = 9.16 Hz), 129.85 (d, J = 21.76 Hz), 130.33 (d, J =
21.44 Hz), 131.54, 131.61, 132.29 (d, J = 27.56 Hz), 134.37, 136.81,
137.08, 138.01, 138.33, 160.37, 179.25 (d, J = 36.86 Hz). MS: m/z (%)
702 (M+2, 3), 700 (M+, 2), 667 (3), 611 (4), 429 (5), 400 (33), 320 (18),
211 (5), 91 (100), 76 (13). Anal. Calcd. for C37H25Cl4N2O2P: C, 63.26;
H, 3.58; N, 3.98. Found: C, 63.29; H, 3.54; N, 3.96.
N-[(10-Nitro-5H,11H-isoindolo[2,1-a]quinoline-5,11-dione)-6-yl]-
iminotricyclohexylphosphorane, 17: This compound was obtained from
(6b) and tricyclohexylphosphine. 82% yield, red solid, m.p. 254◦C;
1
IR: 1715, 1620, 1445. H-NMR: 1.24–1.46 (m, 9H), 1.57–1.70 (m 9H),
1.76–1.91 (m, 12H), 2.30–2.63 (m, 3H), 7.25 (t, J = 8.0 Hz, 1H),
7.57–7.72 (m, 3H), 8.15–8.22 (m, 1H), 9.20-9.33 (m, 2H). 13C-NMR:
26.25, 26.93 (d, J = 45.88 Hz), 27.65 (d, J = 15.28 Hz), 39.16 (d,
J = 235.52 Hz), 117.49, 118.12, 121.09, 121.94, 124.56, 127.16, 128.29,
132.94, 133.85, 136.83, 139.07, 139.18, 139.24, 147.00, 160.13, 178.75
(d, J = 33.64 Hz). MS: m/z (%) 585 (M+, 41), 502 (5), 420 (7), 322 (11),
295 (9), 280 (17), 214 (13), 198 (10), 81 (10), 75 (15), 67 (27), 55 (100).
Anal. Calcd. for C34H40N3O4P: C, 69.74; H, 6.83; N, 7.17. Found: C,
69.89; H, 6.75; N, 7.25.
N-[(9-Nitro-5H,11H-isoindolo[2,1-a]quinoline-5,11-dione)-6-yl]imino-
tricyclohexylphosphorane, 18: This compound was obtained from (6c)
and tricyclohexylphosphine. 70% yield, red solid, m.p. 296◦C; IR: 1718,
1625, 1439. 1H-NMR: 1.31–1.46 (m, 9H), 1.58–1.79 (m, 9H), 1.85–1.98
(m, 12H), 2.41–2.53 (m, 3H), 7.27 (t, J = 8.0 Hz, 1H), 7.68 (t, J = 8.0 Hz,

Iminophosphoranes
387
1H), 8.25 (d, J = 8.8 Hz, 1H), 8.42 (dd, J1 = 8.80 Hz, J2 = 2.0 Hz, 1H),
8.74 (d, J = 2.0 Hz), 9.05 (d, J = 8.0 Hz, 1H), 9.28 (d, J = 8.0 Hz, 1H).
13C-NMR: 26.31, 26.99 (d, J = 48.96 Hz), 27.71 (d, J = 12.24 Hz), 39.16
(d, J = 232.44 Hz), 118.07, 118.56, 120.43, 121.85, 124.66, 127.35,
127.89, 133.45, 133.79, 134.14, 137.25, 138.89, 141.18, 146.16, 160.01,
175.72 (d, J = 33.69 Hz). MS: m/z (%) 585 (M+, 44), 502 (16), 420 (100),
390 (9), 338 (32), 290 (28), 279 (11), 228 (8), 197 (9), 81 (9), 67 (7), 55
(6). Anal. Calcd. for C34H40N3O4P: C, 69.74; H, 6.83; N, 7.17. Found:
C, 69.69; H, 6.79; N, 7.14.
N-[(10-Nitro-5H,11H-isoindolo[2,1-a]quinoline-5,11-dione)-6-yl]-
iminotributylphosphorane, 19: This compound was obtained from (6b)
and tributylphosphine. 50% yield, red solid, m.p. 160◦C; IR: 1712, 1615,
1443. 1H-NMR: 0.86 (t, J = 7.32 Hz, 9H), 1.38–1.43 (m, 6H), 1.46–1.58
(m, 6H), 2.03–2.25 (m, 6H), 7.27 (t, J = 8.0 Hz, 1H), 7.56–7.71 (m,
3H), 8.14 (d, J = 8.05 Hz, 1H), 8.93 (d, J = 8.05 Hz, 1H), 9.19 (d, J =
8.0 Hz, 1H). 13C-NMR: 13.69, 24.15 (d, J = 58.12 Hz), 24.70 (d, J =
15.28 Hz), 28.47 (d, J = 256.92 Hz), 117.70, 118.11, 121.41, 122.13,
124.67, 126.99, 128.26, 130.25, 133.26, 133.96, 136.80, 138.25, 139.00,
146.91, 160.18, 179.25 (d, J = 33.64 Hz). MS: m/z (%) 507 (M+, 58), 477
(10), 450 (8), 321 (8), 291 (20), 279 (13), 263 (23), 244 (27), 189 (30), 147
(23), 92 (100), 75 (62), 63 (60), 55 (85). Anal. Calcd. for C28H34N3O4P:
C, 66.27; H, 6.70; N, 8.28. Found: C, 66.48; H, 6.59; N, 8.18.
N-[(9-Nitro-5H,11H-isoindolo[2,1-a]quinoline-5,11-dione)-6-yl]imino-
tributylphosphorane, 20: This compound was obtained from (6c) and
tributylphosphine. 65% yield, red solid, m.p. 156◦C; IR: 1720, 1624,
1
1435. H-NMR: 0.92 (t, J = 7.4 Hz, 9H), 1.43–1.51 (m, 6H), 1.55–1.74
(m, 6H), 2.09–2.25 (m, 6H), 7.29 (t, J = 8.04 Hz, 1H), 7.71 (d, J =
8.04 Hz, 1H), 8.28 (d, J = 8.8 Hz, 1H), 8.52 (dd, J1 = 8.8 Hz, J2 =
1.8 Hz, 1H), 8.74 (d, J = 8.04 Hz, 1H), 9.05 (d, J = 1.8 Hz, 1H), 9.28 (d,
J = 8.04 Hz, 1H). 13C-NMR: 13.70, 24.25 (d, J = 58.20 Hz), 24.91 (d,
J = 15.16 Hz), 29.62 (d, J = 256.95 Hz), 118.01, 118.70, 122.15, 122.93,
124.70, 127.32, 128.61, 129.78, 133.85, 134.39, 137.45, 138.91, 139.13,
145.73, 162.03, 179.63 (d, J = 33.63 Hz). MS: m/z (%) 507 (M+, 100),
478 (20), 377 (21), 355 (15), 291 (21), 263 (28), 235 (42), 103 (12), 76
(16). Anal. Calcd. for C28H34N3O4P: C, 66.27; H, 6.70; N, 8.28. Found:
C, 66.35; H, 6.63; N, 8.22.
N-[(10-Nitro-5H,11H-isoindolo[2,1-a]quinoline-5,11-dione)-6-yl]-
iminotrimethoxyphosphorane, 21: This compound was obtained from
(6b) and trimethylphosphite. 73% yield, pale yellow solid, m.p. 210◦C;
IR: 1726, 1634, 1466. 1H-NMR: 3.85 (d, J = 11.72 Hz, 9H), 7.32 (t, J =
7.32 Hz, 1H), 7.65–7.98 (m, 3H), 8.25 (d, J = 7.32 Hz, 1H), 9.01 (d,
J = 7.32 Hz, 1H), 9.16 (d, J = 8.79 Hz, 1H). 13C-NMR: 55.13 (d, J =
27.56 Hz), 117.98, 118.79, 122.24, 122.90, 125.19, 127.25, 127.65,

388
H. Z. Alkhathlan et al.
128.89, 133.46, 134.03, 134.27, 136.69, 138.59, 146.86, 160.46, 177.90
(d, J = 33.64 Hz). MS: m/z (%) 429 (M+, 30), 353 (2), 305 (6), 279 (4),
246 (7), 229 (10), 217 (12), 177 (18), 166 (100), 150 (23), 109 (54), 93
(59), 76 (21). Anal. Calcd. for C19H16N3O7P: C, 53.14; H, 3.73; N, 9.79.
Found: C, 53.32; H, 3.65; N, 9.74.
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