A Convenient One-Pot Synthesis of 1,2-Azaphospholanium Salts 601
3
-(Diphenylphosphoryl)propylammonium
combined organic layers were washed with water,
Chloride (13a)
dried over Na
2
SO , and concentrated to solid, which
4
was triturated with ether, filtered off, and dried in
From 0.85 g (3.8 mmol) of diphenylchlorophos-
phine, 0.50 g (3.8 mmol) of 3-chloropropylamine hy-
drochloride, and 0.84 g (8.3 mmol) of triethylamine
in 30 ml of the benzene–chloroform solution, under
conditions previously described for the synthesis of
◦
vacuo to give 0.23 g of 15. Yield 77%, mp 78–81 C. IR
−
1
(
KBr) ν(cm ): 1172 (P O), 1628, 3309, 3372 (NH
2
).
): δ 1.29 (br.
P); 2.27–2.34
P); 2.76 (t, JHH = 6.8 Hz, 2H, CH N);
.42–7.75 (m, 10H, C ). C NMR (CDCl ): δ 21.6
3
1
1
P NMR (CDCl
s, 2H, NH ); 1.68–1.77 (m, 2H, CH
3
): δ 33.1. H NMR (CDCl
CH
3
2
2
2
3
(
7
m, 2H, CH
2
2
6
c, the reaction mixture containing 86.3% of chlo-
1
3
6
H
5
1
3
3
1
ride 6a was obtained ( P NMR spectroscopy data).
The solvents were evaporated in vacuo, and 0.62 g of
(
(
s, CH
2
CH
2
P); 26.6 (d, JCP = 71.5 Hz, CH
2
P); 40.5
3
3
d, JCP = 14.2 Hz, CH
2
N); 128.6 (d, JCP = 11.8 Hz,
1
3a was isolated by crystallization of residue from
2
4
C
1
meta), 130.6 (d, JCP = 9.5 Hz, Cortho), 131.8 (d, JCP
=
ethanol–acetonitrile–ethyl acetate. Yield 55.4%, mp
1
.7 Hz, Cpara), 132.0 (d, JCP = 99.2 Hz, Cipso) (C
Anal. Calcd for C15 18NOP: C, 69.48; H, 7.00; N,
.40; P, 11.95%. Found: C, 69.28; H, 7.01; N, 5.16;
6
H ).
5
◦
−1
183–184 C. IR (KBr) ν(cm ): 1180 (P O), 2400–
H
+
31
1
3
200 (NH
3
). P NMR (CD
3
OD): δ 38.0. H NMR
CH P); 2.75–2.82
P); 3.27 (m, JHH = 7.4 Hz, 2H, CH N);
.74–8.02 (m, 10H, 2C ). C NMR (CD OD): δ 20.4
P); 40.3
5
(
(
CD
m, 2H, CH
3
OD): δ 2.07–2.17 (m, 2H, CH
2
2
P, 11.95%.
3
2
2
1
3
7
6
H
5
1
3
X-Ray Crystal Structure Determination of 8d
At 298 K, crystals of C H ClNO P (M = 525.88) are
(s, CH
2
CH
2
P); 26.4 (d, JCP = 70.1 Hz, CH
2
3
3
(
C
d, JCP = 15.4 Hz, CH
2
N); 129.4 (d, JCP = 12.0 Hz,
2
7
26
4
2
2
1
meta), 131.1 (d, JCP = 9.8 Hz, Cortho), 131.9 (d, JCP
=
˚
3
orthorhombic. Space group P2
1
2
1
˚
2
1
, a = 8.271(4) A,
99.1 Hz, Cipso), 132.8 (s, Cpara) (C
6
H
5
). Anal. Calcd for
˚
˚
b = 13.602(7) A, c = 22.968(9) A, V = 2584(2) A ,
C
15
H19ClNOP: C, 60.92; H, 6.48; N, 4.74; P, 10.47%.
−3
−1
Z = 4, dcalc = 1.352 g cm , µ(Mo Kꢂ) = 3.06 m ,
F(000) = 1096. Intensities of 13,338 reflections were
Found: C, 60.98; H, 6.43; N, 4.65; P, 10.47%.
measured with a SMART 1000 CCD diffractometer at
˚
1
10 K (λ(Mo Kꢂ) = 0.71072 A, ꢀ-scans with 0.3 step
Hydrolysis of 6c and Preparation
of 3-(Diphenylphosphoryl)propylammonium
Iodide (13c)
◦
in ꢀ and 20 s per frame exposure, 2θ < 52 ), and 5044
independent reflections (Rint = 0.0386) were used in
further refinement. The structure was solved by di-
rect method and refined by the full-matrix least-
A solution of 0.30 g (0.81 mmol) of 6c in 24 ml of
ethanol–water (1:1) solution was allowed to stand
for several hours at 20 C, and the solvents were
2
squares technique against F in the anisotropic–
◦
isotropic approximation. The refinement converged
evaporated in vacuo. After crystallization of residue
from the mixture of ethanol–acetonitrile–ethyl ac-
etate, 0.18 g of 13c was obtained. Yield 58.1%, mp
to wR = 0.1454 and GOF = 1.084 for all indepen-
2
dent reflections (R = 0.0590 was calculated against
1
F for 2983 observed reflections with I > 2σ(I)). All
◦
−1
1
2
90–192 C. IR (KBr), ν(cm ): 1162 (P O), 1610,
calculations were performed using SHELXTL PLUS
5.0 on IBM PC/AT. Crystallographic data (exclud-
ing structure factors) for the reported in this pa-
per structure have been deposited to the Cambridge
Crystallographic Data Centre as supplementary no.
CCDC-209266. Copies of the data can be obtained
free of charge on application to CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK (Fax: (internat.) +44-
1223/336-033; e-mail: deposit@ccdc.cam.ac.uk).
+
31
1
300–3300 (NH
OD): δ 1.91–2.01 (m, 2H, CH
.70 (m, 2H, CH P); 3.12–3.17 (m, 2H, CH
.89 (m, 10H, C
3
). P NMR (CD
3
OD): δ 37.8. H
CH P); 2.62–
N); 7.61–
OD): δ 20.4
NMR (CD
2
7
3
2
2
2
2
1
3
6
H
5
). C NMR (CD
3
1
(s, CH
2
CH
2
P); 26.5 (d, JCP = 72.0 Hz, CH
2
P); 40.3
3
3
(
C
d, JCP = 14.8 Hz, CH
2
N); 129.4 (d, JCP = 12.0 Hz,
2
1
meta), 131.1 (d, JCP = 9.8 Hz, Cortho), 131.8 (d, JCP
=
4
1
00.9 Hz, Cipso), 132.9 (d, JCP < 3.6 Hz, Cpara) (C
6
5
H ).
Anal. Calcd for C15 19INOP: C, 46.53; H, 4.94; N,
H
3
8
.66; P, 8.00%. Found: C, 46.39; H, 4.87; N, 3.77; P,
.00%.
REFERENCES
[
[
[
1] Sakai, T.; Kodama, T.; Fujimoto, T.; Ohta, K.;
Yamamoto, I. J Org Chem 1994, 59, 7144.
2] Yamamoto, I.; Tashiro, K.; Uchiyama, T.; Fujimoto, T.
Phosphorus Sulfur Silicon 1999, 148, 11.
3] Uchiyama, T.; Inoue, M.; Masuda, H.; Fujimoto, T.;
Yamamoto, I. Phosphorus Sulfur Silicon 2001, 175,
Alkaline Hydrolysis of 6d and Preparation of
3-Aminopropyl)diphenylphosphine Oxide (15)
(
To a solution of 0.4 g (1.17 mmol) of perchlorate 6d
in 35 ml of H O, 7.3 ml of 0.2 N aqueous NaOH was
added. The reaction mixture was evaporated up to 8–
0 ml and extracted with chloroform (3 × 10 ml). The
9
9.
2
[
4] Sakai, T.; Uchiyama, T.; Fujimoto, T.; Ohta, K.;
Yamamoto, I.; Kakehi, A. Heterocycl Commun 1996,
2, 233.
1