Vinyltriphenylphosphonium salt mediated serendipitous synthesis of aryliminophosphoranes

Article abstract of DOI:10.1016/S0040-4020(02)00788-3

Crystalline phosphorus ylides are obtained in excellent yields from the 1:1:1 addition reaction between triphenylphosphine, dimethyl acetylenedicarboxylate and aromatic amines, such as aniline, 1-naphthylamine, p-toluidine, 4-bromoaniline, 4-nitroaniline, 4-acetylaniline, 2-aminopyridine, or 2-amino-5-bromopyridine. These stabilized phosphoranes undergo a smooth intramolecular reaction in boiling p-xylene or toluene to produce aryliminophosphoranes in excellent yields.

Full text of DOI:10.1016/S0040-4020(02)00788-3

Tetrahedron 58 (2002) 7213–7219
Vinyltriphenylphosphonium salt mediated serendipitous synthesis
of aryliminophosphoranes
*
Issa Yavari, Mehdi Adib and Leila Hojabri
Department of Chemistry, University of Tarbiat Modarres, P.O. Box 14115-175, Tehran, Iran
Received 1 January 2002; revised 12 June 2002; accepted 4 July 2002
Abstract—Crystalline phosphorus ylides are obtained in excellent yields from the 1:1:1 addition reaction between triphenylphosphine,
dimethyl acetylenedicarboxylate and aromatic amines, such as aniline, 1-naphthylamine, p-toluidine, 4-bromoaniline, 4-nitroaniline,
4-acetylaniline, 2-aminopyridine, or 2-amino-5-bromopyridine. These stabilized phosphoranes undergo a smooth intramolecular reaction in
boiling p-xylene or toluene to produce aryliminophosphoranes in excellent yields. q 2002 Elsevier Science Ltd. All rights reserved.
1. Introduction
arylphosphines with dimethyl acetylenedicarboxylate
(DMAD), and on occasion, other acetylenic systems have
been discussed.11,12 We report here an efficient synthetic
route to aryliminophosphoranes using triphenylphosphine,
DMAD, and aromatic amines such as aniline (a),
1-naphthylamine (b), p-toluidine (c), 4-bromoaniline (d),
4-nitroaniline (e), 4-acetylaniline (f), 2-aminopyridine (g),
or 2-amino-5-bromopyridine (h). Thus, reaction of aromatic
amines 1a–h with DMAD in the presence of triphenyl-
phosphine leads to the corresponding stable phosphorus
ylides 2, which undergo a smooth transformation in boiling
p-xylene or toluene to produce iminophosphorane 3,
dimethyl fumarate and dimethyl maleate 4 (see Scheme 1).
Iminophosphoranes, compounds of general structure
R3PvNR0 with four-coordinate phosphorus and incorporat-
ing a formal phosphorus–nitrogen double bond, are reactive
species, which take part in many valuable reactions in
organic synthesis.1 – 4 Iminophosphoranes were first
reported by Staudinger and Meyer6 in 1919 but virtually
no additional chemistry was reported until the early 1960s.
Much chemistry has been discovered in the last three
decades with numerous applications to organic syn-
thesis.1–5 Several methods have been developed for the
preparation of iminophosphoranes.1–10 Reactions of tri-
Scheme 1.
Keywords: aryliminophosphoranes; triphenylphosphine; stable phosphorus ylides; acetylenic esters.
*
Corresponding author. Tel.: þ98-21-8006631; fax: þ98-21-8006544; e-mail: isayavar@yahoo.com
0040–4020/02/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(02)00788-3

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I. Yavari et al. / Tetrahedron 58 (2002) 7213–7219
Table 1. Selected 1H, 13C, and 31P NMR chemical shifts (d in ppm) and coupling constants (J in Hz) for H-2, CO2CH3, OCH3, C-2, C-3, and P in the major (M)
and minor (m) geometrical isomers of compounds 2a–h
Compound
Ar
Isomer (%)
1H NMR spectroscopic data
13C NMR spectroscopic data
C-2 (2JPC C-3 (1JPC
)
31P
H-2 (3JPH
)
OCH3
CO2CH3
)
2a
2b
M (74)
m (26)
4.29 (16.3)
4.16 (16.9)
3.09
3.61
3.68
3.65
56.91 (13.9)
56.21 (15.1)
42.74 (123.4)
44.05 (136.1)
21.93
22.60
M (75)
m (25)
4.58 (17.0)
4.39 (16.8)
3.14
3.62
3.69
3.67
56.95 (13.3)
56.43 (13.8)
42.66 (123.6)
44.05 (136.0)
21.77
22.43
2c
M (71)
m (29)
4.19 (14.7)
4.11 (15.5)
3.08
3.61
3.68
3.66
57.52 (14.0)
56.74 (12.7)
42.68 (124.0)
43.95 (131.2)
21.91
22.52
2d
2e
M (73)
m (27)
4.25 (17.0)
4.09 (17.5)
3.10
3.60
3.68
3.65
56.73 (14.2)
56.10 (15.5)
42.36 (124.1)
43.74 (130.5)
21.74
22.61
M (74)
m (26)
4.43 (16.3)
4.23 (17.2)
3.16
3.62
3.70
3.68
55.46 (15.4)
54.95 (16.5)
42.36 (125.3)
43.52 (137.0)
21.64
22.88
2f
M (75)
m (25)
4.42 (17.5)
4.24 (17.1)
3.14
3.62
3.68
3.66
55.38 (14.8)
54.85 (14.7)
42.56 (124.9)
43.75 (136.1)
21.80
22.84
2g
2h
M (69)
m (31)
4.86 (16.3)
4.67 (17.4)
3.11
3.59
3.68
3.66
53.76 (16.2)
53.33 (15.9)
43.43 (125.9)
44.34 (134.0)
22.50
23.40
M (74)
m (26)
4.77 (15.7)
4.66 (17.0)
3.11
3.57
3.68
3.66
53.89 (16.3)
53.37 (16.4)
43.16 (126.0)
44.07 (135.1)
22.51
23.48
1
2. Results and discussion
consistent with the presence of two isomers. Selected H,
13C and 31P NMR chemical shifts and coupling constants of
the major (M) and minor (m) geometrical isomers of
compounds 2a–h are shown in Table 1. The ylide moiety of
these compounds is strongly conjugated with the adjacent
carbonyl group and rotation about the partial double bond in
2-(E ) and 2-(Z) (see Scheme 2) is slow on the NMR
timescale at ambient temperature.
The reaction of aromatic amines 1a–h (see Scheme 1) with
DMAD in the presence of triphenylphosphine proceeded
spontaneously at room temperature in dichloromethane, and
1
finished within 2 h. H and 13C NMR spectra of the crude
product clearly indicated the formation of phosphorane 2.
Any product other than 2 could not be detected by NMR
spectroscopy.
The structures of compounds 2a–h were deduced from their
1
elemental analyses and their high-field H, 13C, and 31P
NMR and IR spectral data. The nature of these compounds
as 1:1:1 adducts were apparent from their mass spectra
which displayed molecular ion peaks. Initial fragmentation
involves loss from or complete loss of the side chains.
1
The H, 13C, and 31P NMR spectra of ylides 2a–h are
Scheme 2.

I. Yavari et al. / Tetrahedron 58 (2002) 7213–7219
7215
Scheme 3.
On the basis of the well established chemistry of trivalent
phosphorus nucleophiles,2,13–19 it is reasonable to assume
that phosphorus ylide 2 results from the initial addition of
triphenylphosphine to the acetylenic ester and subsequent
protonation of the 1:1 adduct by the NH-acid 1. Then the
Michael acceptor is attacked by the nitrogen atom of the
conjugate base of the NH-acid to form phosphorane 2 (see
Scheme 3).
4-nitroaniline, 4-acetylaniline and 2-aminopyridine were
obtained from Fluka (Buchs, Switzerland) and were used
without further purification. 2-Amino-5-bromopyridine was
prepared according to literature.20 Melting points were
measured on an Electrothermal 9100 apparatus. Elemental
analyses for C, H and N were performed using a Heraeus
CHN-O-Rapid analyzer. Mass spectra were recorded on a
FINNIGAN-MATT 8430 mass spectrometer operating at an
ionization potential of 70 eV. 1H, 13C and 31P NMR spectra
were measured (CDCl3 solution) with a Brucker DRX-500
AVANCE spectrometer at 500.1, 125.8 and 202.5 MHz,
respectively. IR spectra were recorded on a Shimadzu
IR-460 spectrometer.
Phosphorus ylides 2 undergo a smooth, and clean, reaction
in boiling p-xylene or toluene to produce iminophosphorane
3 and dimethyl fumarate and/or dimethyl maleate
(Scheme 1). Structure 3 was assigned to the isolated
products on the basis of their elemental analyses and IR, 1H,
13C and 31P NMR and mass spectral data. The mass spectra
of iminophosphoranes 3 confirm their molecular weights.
3.1. General procedure for preparation of compounds
2a–h
1
Partial assignments of the H, 13C and 31P resonances in
1
the H, 13C and 31P NMR spectra of 3a–h are given in
Section 3.
3.1.1. Dimethyl 2-anilino-3-(triphenylphosphoranyl-
idene)butanedioate 2a. The process for the preparation of
the title compound is described as an example. To a
magnetically stirred solution of triphenylphosphine
(0.524 g, 2 mmol) and aniline (0.186 g, 2 mmol) in
dichloromethane (4 mL) was added dropwise a mixture of
DMAD (0.284 g, 2 mmol) in dichloromethane (2 mL) at
258C over 10 min. The reaction mixture was then allowed
to warm up to room temperature and stirred for 2 h. The
solvent was removed under reduced pressure and the
residual solid recrystallized from 1:1 hexane–ethyl acetate
as pale yellow crystals, mp 192–1958C, 0.97 g, yield 98%.
IR (KBr) (nmax/cm21): 3368 (NH), 1730 and 1613 (CvO).
MS, m/z (%): 497 (Mþ, 6), 435 (20), 405 (8), 383 (29), 303
(10), 262 (100), 183 (37), 78 (20). Anal. Calcd for
C30H28NO4P (497.53): C, 72.42; H, 5.67; N, 2.82. Found:
C, 72.4; H, 5.7; N, 2.8%.
Although we have not established the mechanism of the
formation of iminophosphoranes 3 from ylides 2 in an
experimental manner, it is reasonable to assume that in
boiling p-xylene or toluene, the NH-proton shifts to the
ylidic carbon and forms the phosphorus betaine 5. This
betaine can be in equilibrium with the azaphosphetane.
Iminophosphorane 3 is formed from fragmentation of the
azaphosphetane 6. Formation of dimethyl fumarate and/or
dimethyl maleate confirms the proposed mechanism
(Scheme 3).
In summary, the present synthesis of iminophosphoranes
complements older methods1–10 and offers significant
advantages for the synthesis of iminophosphoranes from
aromatic amines. The present method carries the advantage
that, not only is the reaction performed under neutral
conditions, but also that the substances can be mixed
without any activation or modification. The procedure
described here may be an acceptable method for the
preparation of aryliminophosphoranes with variable
functionalities.
Major isomer, 2a-(Z) (74%), 1H NMR: d 3.09 and 3.68 (6H,
2s, 2OCH3), 4.29 (1H, br d, 3JPH¼16.3 Hz, P–C–CH), 5.35
(1H, br, NH), 6.27 (2H, d, J¼7.5 Hz, 2CH), 7.00 (2H, t,
J¼7.1 Hz, 2CH), 7.08 (1H, t, J¼7.2 Hz, CH), 7.3–7.6 (15H,
1
m, 3C6H5). 13C NMR: d 42.74 (d, JPC¼123.4 Hz, PvC),
2
48.85 and 51.94 (2OCH3), 56.91 (d, JPC¼13.9 Hz, P–C–
1
C H), 115.21 (CH), 117.78 (C), 126.90 (d, JPC¼91.8 Hz,
3
C
ipso), 128.50 (d, JPC¼12.5 Hz, Cm), 129.19 (CH),
131.95 (d, JPC¼2.3 Hz, Cp), 133.80 (d, JPC¼9.7 Hz, Co),
4
2
3. Experimental
2
147.60 (C–N), 169.73 and 174.66 (2d, JPC¼7.7 Hz
and JPC¼12.8 Hz, 2CvO ester). 31P NMR: d 21.93
3
Dimethyl acetylenedicarboxylate, triphenylphosphine,
aniline, 1-naphthylamine, p-toluidine, 4-bromoaniline,
(Ph3PvC).

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I. Yavari et al. / Tetrahedron 58 (2002) 7213–7219
Minor isomer, 2a-(E) (26%), 1H NMR: d 3.61 and 3.65 (6H,
2s, 2OCH3), 4.16 (1H, br d, 3JPH¼16.9 Hz, P–C–CH), 4.85
(1H, br, NH), 6.18 (2H, d, J¼7.0 Hz, 2CH), 6.65 (2H, t,
J¼7.0 Hz, 2CH), 6.67 (1H, t, J¼7.1 Hz, CH), 7.3–7.6 (15H,
2CH), 7.3–7.6 (15H, m, 3C6H5). 13C NMR: d 20.47 (CH3),
42.68 (d, 1JPC¼124.0 Hz, PvC), 48.79 and 51.87 (2OCH3),
2
57.52 (d, JPC¼14.0 Hz, P–C–C H), 115.80 (CH), 126.95
1
(d, JPC¼91.4 Hz, Cipso), 127.06 (C), 128.45 (d,
m, 3C6H5). 13C NMR: d 44.05 (d, JPC¼136.1 Hz, PvC),
3JPC¼12.3 Hz, Cm), 129.26 (CH), 131.89 (Cp), 133.77 (d,
2JPC¼9.6 Hz, Co), 145.40 (C–N), 169.58 and 174.72 (2d,
2JPC¼7.9 Hz and 3JPC¼12.6 Hz, 2CvO ester). 31P NMR: d
21.91 (Ph3PvC).
1
2
50.08 and 51.85 (2OCH3), 56.21 (d, JPC¼15.1 Hz, P–C–
1
C H), 115.07 (CH), 117.91 (C), 126.33 (d, JPC¼90.6 Hz,
3
C
ipso), 128.54 (d, JPC¼12.2 Hz, Cm), 129.12 (CH),
131.90 (d, JPC¼2.2 Hz, Cp), 133.74 (d, JPC¼9.6 Hz,
4
2
Co), 147.54 (C–N), 170.01 and 174.60 (2d, JPC¼7.6 Hz
Minor isomer, 2c-(E ) (29%), 1H NMR: d 2.22 (3H, s, CH3),
3.61 and 3.66 (6H, 2s, 2OCH3), 4.11 (1H, dd, 3JPH¼15.5 Hz
and 3JHH¼6.9 Hz, P–C–CH), 4.77 (1H, br d, 3JHH¼6.9 Hz,
NH), 6.11 (2H, d, J¼7.3 Hz, 2CH), 6.84 (2H, d, J¼7.3 Hz,
2CH), 7.3–7.6 (15H, m, 3C6H5). 13C NMR: d 20.43 (CH3),
43.95 (d, 1JPC¼131.2 Hz, PvC), 50.02 and 51.86 (2OCH3),
2
and JPC¼14.5 Hz, 2CvO ester). 31P NMR: d 22.60
3
(Ph3PvC).
3.1.2. Dimethyl 2-(1-naphthylamino)-3-(triphenylphos-
phoranylidene) butanedioate 2b. Pale yellow crystals,
mp 180–1838C, 1.07 g, yield 98%. IR (KBr) (nmax/cm21):
3390 (NH), 1730, 1614 (CvO). MS, m/z (%): 547 (Mþ, 3),
485 (14), 459 (10), 405 (8), 262 (100), 183 (66), 108 (42),
78 (36), 51 (31). Anal. Calcd for C34H30NO4P (547.59):
C, 74.58; H, 5.52; N, 2.56. Found: C, 74.6; H, 5.5; N,
2.6%.
2
56.74 (d, JPC¼12.7 Hz, P–C–C H), 115.71 (CH), 126.36
1
(d, JPC¼91.8 Hz, Cipso), 127.25 (C), 128.55 (d,
3JPC¼12.2 Hz, Cm), 129.24 (CH), 131.88 (Cp), 133.72 (d,
2JPC¼9.6 Hz, Co), 145.26 (C–N), 170.34 and 174.65 (2d,
2JPC¼7.8 Hz and 3JPC¼14.5 Hz, 2CvO ester). 31P NMR: d
22.52 (Ph3PvC).
Major isomer, 2b-(Z ) (75%), 1H NMR: d 3.14 and 3.69 (6H,
2s, 2OCH3), 4.58 (1H, dd, 3JPH¼17.0 Hz and 3JHH¼7.0 Hz,
P–C–CH), 6.18 (2H, br, NH and CH), 7.15 (2H, br, 2CH),
7.3–7.6 (17H, m, 3C6H5 and 2CH), 7.70 (1H, d, J¼8.0 Hz,
CH), 7.84 (1H, d, J¼8.0 Hz, CH). 13C NMR: d 42.66 (d,
1JPC¼123.6 Hz, PvC), 48.96 and 51.99 (2OCH3), 56.95 (d,
2JPC¼13.3 Hz, P–C–CH), 107.29, 117.44, 121.31 and
3.1.4. Dimethyl 2-(4-bromoanilino)-3-(triphenylphos-
phoranylidene)butanedioate 2d. Pale orange crystals, mp
178–1818C, 1.01 g, yield 96%. IR (KBr) (nmax/cm21): 3365
(NH), 1728, 1609 (CvO). MS, m/z (%): 577 (Mþþ2, 9),
575 (Mþ, 11), 405 (14), 262 (100), 183 (72), 108 (49), 79
(36). Anal. Calcd for C30H27BrNO4P (576.43): C, 62.51; H,
4.72; N, 2.43. Found: C, 62.6; H, 4.7; N, 2.5%.
1
124.31 (4CH), 124.99 (d, JPC¼91.1 Hz, Cipso), 125.35
(CH), 126.32 and 127.10 (2C), 128.14 (CH), 128.44 (d,
3JPC¼12.1 Hz, Cm), 131.91 (d, 4JPC¼2.0 Hz, Cp), 133.68 (d,
2JPC¼9.8 Hz, Co), 134.42 (CH), 142.86 (C–N), 170.00 and
174.75 (2d, 2JPC¼6.5 Hz and 3JPC¼12.1 Hz, 2CvO ester).
31P NMR: d 21.77 (Ph3PvC).
Major isomer, 2d-(Z) (73%), 1H NMR: d 3.10 and 3.68 (6H,
2s, 2OCH3), 4.25 (1H, dd, 3JPH¼17.0 Hz and 3JHH¼7.9 Hz,
P–C–CH), 5.36 (1H, br d, 3JHH¼7.9 Hz, NH), 6.15 (2H, d,
J¼8.0 Hz, 2CH), 7.09 (2H, d, J¼8.0 Hz, 2CH), 7.3–7.6
1
(15H, m, 3C6H5). 13C NMR: d 42.36 (d, JPC¼124.1 Hz,
2
PvC), 48.88 and 51.97 (2OCH3), 56.73 (d, JPC¼14.2 Hz,
Minor isomer, 2b-(E ) (25%), 1H NMR: d 3.62 and 3.67 (6H,
2s, 2OCH3), 4.39 (1H, dd, 3JPH¼16.8 Hz and 3JHH¼7.0 Hz,
P–C–CH), 5.68 (1H, br d, J¼7.0 Hz, NH), 5.96 (1H, br d,
J¼7.5 Hz, CH), 7.07 (1H, br t, J¼7.0 Hz, CH), 7.13 (1H, br
t, J¼6.9 Hz, CH), 7.2–7.6 (17H, m, 3C6H5 and 2CH), 7.74
(1H, d, J¼8.0 Hz, CH), 7.79 (1H, d, J¼8.0 Hz, CH). 13C
P–C–C H), 109.25 (C–Br), 116.61 (CH), 126.65 (d,
3
1JPC¼91.8 Hz, Cipso), 128.50 (d, JPC¼12.3 Hz, Cm),
4
131.42 (CH), 132.01 (d, JPC¼2.1 Hz, Cp), 133.63 (d,
2JPC¼9.8 Hz, Co), 146.56 (C–N), 169.72 and 174.23 (2d,
2JPC¼6.6 Hz and 3JPC¼12.8 Hz, 2CvO ester). 31P NMR: d
21.74 (Ph3PvC).
1
NMR: d 44.05 (d, JPC¼136.0 Hz, PvC), 50.14 and 51.92
2
(2OCH3), 56.43 (d, JPC¼13.8 Hz, P–C–C H), 107.14,
Minor isomer, 2d-(E ) (27%), 1H NMR: d 3.60 and 3.65 (6H,
2s, 2OCH3), 4.09 (1H, br d, 3JPH¼17.5 Hz, P–C–CH), 4.85
(1H, br, NH), 6.05 (2H, d, J¼7.9 Hz, 2CH), 7.05 (2H, d,
J¼7.9 Hz, 2CH), 7.3–7.6 (15H, m, 3C6H5). 13C NMR: d
43.74 (d, 1JPC¼130.5 Hz, PvC), 50.06 and 51.94 (2OCH3),
117.65, 120.74 and 124.38 (4CH), 126.18 (d, 1JPC¼93.5 Hz,
C
ipso), 125.30 (CH), 126.30 and 127.12 (2C), 128.10 (CH),
128.46 (d, 3JPC¼12.1 Hz, Cm), 131.90 (d, 4JPC¼2.0 Hz, Cp),
133.70 (d, JPC¼9.8 Hz, Co), 134.35 (CH), 142.74 (C–N),
2
2
3
2
170.25 and 174.70 (2d, JPC¼6.4 Hz and JPC¼12.0 Hz,
2CvO ester). 31P NMR: d 22.43 (Ph3PvC).
56.10 (d, JPC¼15.5 Hz, P–C–C H), 109.22 (C–Br),
1
116.31 (CH), 126.12 (d, JPC¼90.7 Hz, Cipso), 128.58 (d,
4
3JPC¼12.3 Hz, Cm), 131.40 (CH), 132.06 (d, JPC¼2.0 Hz,
2
3.1.3. Dimethyl 2-(4-methylanilino)-3-(triphenylphos-
phoranylidene)butanedioate 2c. Pale yellow crystals, mp
180–1838C, 1.00 g, yield 98%. IR (KBr) (nmax/cm21): 3410
(NH), 1731, 1596 (CvO). MS, m/z (%): 511 (Mþ, 9), 459
(10), 449 (13), 405 (10), 262 (100), 183 (49), 108 (51), 78
(44), 51 (39). Anal. Calcd for C31H30NO4P (511.56): C,
72.79; H, 5.91; N, 2.74. Found: C, 72.8; H, 5.9; N, 2.7%.
Cp), 133.60 (d, JPC¼9.7 Hz, Co), 146.46 (C–N), 170.20
2
3
and 174.15 (2d, JPC¼6.6 Hz and JPC¼14.1 Hz, 2CvO
ester). 31P NMR: d 22.61 (Ph3PvC).
3.1.5. Dimethyl 2-(4-nitroanilino)-3-(triphenylphosphor-
anylidene)butanedioate 2e. Pale yellow crystals, mp 209–
2118C, 1.06 g, yield 98%. IR (KBr) (nmax/cm21): 3370
(NH), 1723, 1608, 1586 (CvO). MS, m/z (%): 542 (Mþ, 2),
530 (5), 483 (100), 451 (20), 405 (74), 303 (20), 262
(60), 183 (45), 108 (32). Anal. Calcd for C30H27N2O6P
(542.53): C, 66.42; H, 5.02; N, 5.16. Found: C, 66.5; H, 5.1;
N, 5.1%.
Major isomer, 2c-(Z ) (71%), 1H NMR: d 2.20 (3H, s, CH3),
3.08 and 3.68 (6H, 2s, 2OCH3), 4.19 (1H, dd, 3JPH¼14.7 Hz
and 3JHH¼7.0 Hz, P–C–CH), 5.28 (1H, br d, 3JHH¼7.0 Hz,
NH), 6.20 (2H, d, J¼7.7 Hz, 2CH), 6.82 (2H, d, J¼7.7 Hz,

I. Yavari et al. / Tetrahedron 58 (2002) 7213–7219
7217
Major isomer, 2e-(Z ) (74%), 1H NMR: d 3.16 and 3.70 (6H,
2s, 2OCH3), 4.43 (1H, dd, 3JPH¼16.3 Hz and 3JHH¼8.0 Hz,
78 (20). Anal. Calcd for C29H27N2O4P (498.52): C, 69.87;
H, 5.46; N, 5.62. Found: C, 69.9; H, 5.5; N, 5.6%.
3
P–C–CH), 6.08 (1H, d, JHH¼8.0 Hz, NH), 6.15 (2H, d,
J¼8.5 Hz, 2CH), 7.4–7.7 (15H, m, 3C6H5), 7.93 (2H, d,
Major isomer, 2g-(Z) (69%), 1H NMR: d 3.11 and 3.68 (6H,
2s, 2OCH3), 4.86 (1H, dd, 3JPH¼16.3 Hz and 3JHH¼9.2 Hz,
1
J¼8.5 Hz, 2CH). 13C NMR: d 42.36 (d, JPC¼125.3 Hz,
2
3
PvC), 49.21 and 52.36 (2OCH3), 55.46 (d, JPC¼15.4 Hz,
P–C–CH), 6.15 (1H, d, JHH¼9.2 Hz, NH), 6.40 (2H, m,
P–C–C H), 111.68 (CH), 126.12 (CH), 126.27 (d,
2CH), 7.25 (1H, m, CH), 7.4–7.7 (15H, m, 3C6H5), 7.66
(1H, d, J¼7.7 Hz, CH). 13C NMR: d 43.43 (d,
1JPC¼125.9 Hz, PvC), 48.86 and 52.01 (2OCH3), 53.76
3
1JPC¼92.0 Hz, Cipso), 128.80 (d, JPC¼12.2 Hz, Cm),
2
132.40 (Cp), 133.62 (d, JPC¼9.4 Hz, Co), 137.62 and
2
2
152.33 (2C–N), 170.15 and 173.46 (2d, JPC¼6.9 Hz and
(d, JPC¼16.2 Hz, P–C–C H), 109.15 and 112.37 (2CH),
3JPC¼12.2 Hz, 2CvO ester). 31P NMR: d 21.64 (Ph3PvC).
127.07 (d, JPC¼92.1 Hz, Cipso), 128.42 (d, JPC¼12.3 Hz,
1
3
Cm), 131.86 (Cp), 133.82 (d, JPC¼9.8 Hz, Co), 136.54 and
2
Minor isomer, 2e-(E ) (26%), 1H NMR: d 3.62 and 3.68 (6H,
147.24 (2CH), 157.91 (NvC–N), 170.15 and 174.81 (2d,
2JPC¼8.3 Hz and 3JPC¼13.0 Hz, 2CvO ester). 31P NMR: d
22.50 (Ph3PvC).
2s, 2OCH3), 4.23 (1H, dd, 3JPH¼17.2 Hz and 3JHH¼8.0 Hz,
3
P–C–CH), 5.57 (1H, d, JHH¼8.0 Hz, NH), 6.10 (2H, d,
J¼8.5 Hz, 2CH), 7.4–7.7 (15H, m, 3C6H5), 7.91 (2H, d,
1
J¼8.5 Hz, 2CH). 13C NMR: d 43.52 (d, JPC¼137.0 Hz,
Minor isomer, 2g-(E) (31%), 1H NMR: d 3.59 and 3.66 (6H,
2s, 2OCH3), 4.67 (1H, dd, 3JPH¼17.4 Hz and 3JHH¼9.1 Hz,
2
PvC), 50.30 and 52.33 (2OCH3), 54.95 (d, JPC¼16.5 Hz,
1
3
P–C–C H), 111.44 (CH), 125.91 (d, JPC¼92.0 Hz, Cipso),
P–C–CH), 5.58 (1H, d, JHH¼9.1 Hz, NH), 6.12 (1H, d,
3
126.14 (CH), 128.82 (d, JPC¼12.1 Hz, Cm), 132.42 (Cp),
J¼7.5 Hz, CH), 6.42 (1H, m, CH), 7.23 (1H, m, CH), 7.4–
7.7 (15H, m, 3C6H5), 7.76 (1H, d, J¼7.6 Hz, CH). 13C
2
133.64 (d, JPC¼9.5 Hz, Co), 137.65 and 152.31 (2C–N),
2
3
1
170.12 and 173.42 (2d, JPC¼7.0 Hz and JPC¼12.4 Hz,
2CvO ester). 31P NMR: d 22.88 (Ph3PvC).
NMR: d 44.34 (d, JPC¼134.0 Hz, PvC), 50.08 and 51.99
2
(2OCH3), 53.33 (d, JPC¼15.9 Hz, P–C–CH), 107.95 and
1
112.53 (2CH), 126.45 (d, JPC¼91.3 Hz, Cipso), 128.58 (d,
2
3.1.6. Dimethyl 2-(4-acetylanilino)-3-(triphenylphos-
phoranylidene)butanedioate 2f. Pale orange crystals, mp
169–1718C, 1.06 g, yield 98%. IR (KBr) (nmax/cm21): 3355
(NH), 1731, 1603 (CvO). MS, m/z (%): 539 (Mþ, 2), 459
(8), 405 (5), 262 (100), 183 (75), 108 (47), 51 (42). Anal.
Calcd for C32H30NO5P (539.57): C, 71.23; H, 5.60; N, 2.60.
Found: C, 71.4; H, 5.6; N, 2.5%.
3JPC¼12.7 Hz, Cm), 131.84 (Cp), 133.80 (d, JPC¼9.5 Hz,
Co), 136.70 and 147.53 (2CH), 157.76 (NvC–N), 170.44
2
3
and 174.79 (2d, JPC¼8.5 Hz and JPC¼18.1 Hz, 2CvO
ester). 31P NMR: d 23.40 (Ph3PvC).
3.1.8. Dimethyl 2-(5-bromo-2-pyridylamino)-3-(tri-
phenylphosphoranylidene) butanedioate 2h. Pale orange
crystals, mp 197–1998C, 1.13 g, yield 98%. IR (KBr)
(nmax/cm21): 3385 (NH), 1713 and 1612 (CvO). MS, m/z
(%): 578 (Mþþ2, 6), 576 (Mþ, 8), 519 (65), 487 (25), 434
(21), 383 (24), 262 (100), 183 (42), 78 (35). Anal. Calcd for
C29H26BrN2O4P (577.41): C, 60.32; H, 4.54; N, 4.85.
Found: C, 60.3; H, 4.5; N, 4.9%.
Major isomer, 2f-(Z) (75%), 1H NMR: d 2.45 (3H, s, CH3),
3.14 and 3.68 (6H, 2s, 2OCH3), 4.42 (1H, dd, 3JPH¼17.5 Hz
and 3JHH¼8.3 Hz, P–C–CH), 5.82 (1H, br d, 3JHH¼8.3 Hz,
NH), 6.21 (2H, d, J¼7.9 Hz, 2CH), 7.4–7.6 (15H, m,
3C6H5), 7.68 (2H, d, J¼7.9 Hz, 2CH). 13C NMR: d 25.91
1
(CH3), 42.56 (d, JPC¼124.9 Hz, PvC), 49.04 and 52.14
2
(2OCH3), 55.38 (d, JPC¼14.8 Hz, P–C–C H), 112.29
Major isomer, 2h-(Z ) (74%), 1H NMR: d 3.11 and 3.68 (6H,
2s, 2OCH3), 4.77 (1H, dd, 3JPH¼15.7 Hz and 3JHH¼9.0 Hz,
1
(CH), 126.43 (C), 126.44 (d, JPC¼92.0 Hz, Cipso), 128.67
3
3
(d, JPC¼12.1 Hz, Cm), 130.43 (CH), 132.22 (Cp), 133.62
P–C–CH), 6.27 (1H, d, JHH¼9.0 Hz, NH), 6.31 (1H, d,
2
3
(d, JPC¼9.4 Hz, Co), 151.31 (C–N), 169.97 and 173.90
3JHH¼8.7 Hz, CH), 7.31 (1H, d, JHH¼8.7 Hz, CH), 7.4–
(2d, 2JPC¼7.4 Hz and 3JPC¼12.6 Hz, 2CvO ester), 196.19
7.6 (15H, m, 3C6H5), 7.66 (1H, s, CH). 13C NMR: d 43.16
(CvO). 31P NMR: d 21.80 (Ph3PvC).
(d, JPC¼126.0 Hz, PvC), 48.93 and 52.09 (2OCH3),
1
2
53.89 (d, JPC¼16.3 Hz, P–C–C H), 106.59 (CH), 110.80
Minor isomer, 2f-(E) (25%), 1H NMR: d 2.47 (3H, s, CH3),
3.62 and 3.66 (6H, 2s, 2OCH3), 4.24 (1H, dd, 3JPH¼17.1 Hz
(C–Br), 126.89 (d, JPC¼92.1 Hz, Cipso), 128.53 (d,
1
2
3JPC¼12.3 Hz, Cm), 132.00 (Cp), 133.80 (d, JPC¼9.8 Hz,
3
3
and JHH¼8.3 Hz, P–C–CH), 5.34 (1H, d, JHH¼8.3 Hz,
NH), 6.14 (2H, d, J¼7.7 Hz, 2CH), 7.4–7.6 (15H, m,
3C6H5), 7.66 (2H, d, J¼7.7 Hz, 2CH). 13C NMR: d 25.89
Co), 138.92 and 147.67 (2CH), 156.46 (NvC–N), 170.15
2
3
and 174.45 (2d, JPC¼8.4 Hz and JPC¼13.2 Hz, 2CvO
ester). 31P NMR: d 22.51 (Ph3PvC).
1
(CH3), 43.75 (d, JPC¼136.1 Hz, PvC), 50.17 and 52.12
2
(2OCH3), 54.85 (d, JPC¼14.7 Hz, P–C–C H), 112.05
Minor isomer, 2h-(E ) (26%), 1H NMR: d 3.57 and 3.66 (6H,
2s, 2OCH3), 4.66 (1H, dd, 3JPH¼17.0 Hz and 3JHH¼8.9 Hz,
1
(CH), 125.96 (d, JPC¼92.0 Hz, Cipso), 126.45 (C), 128.69
3
3
(d, JPC¼12.1 Hz, Cm), 130.41 (CH), 132.21 (Cp), 133.65
P–C–CH), 5.67 (1H, d, JHH¼8.9 Hz, NH), 6.13 (1H, d,
2
3
(d, JPC¼9.4 Hz, Co), 151.29 (C–N), 170.05 and 173.88
3JHH¼8.2 Hz, CH), 7.29 (1H, d, JHH¼8.2 Hz, CH), 7.4–
(2d, 2JPC¼7.3 Hz and 3JPC¼12.6 Hz, 2CvO ester), 196.15
7.6 (15H, m, 3C6H5), 7.72 (1H, s, CH). 13C NMR: d 44.07
(CvO). 31P NMR: d 22.84 (Ph3PvC).
(d, 1JPC¼135.1 Hz, PvC), 50.11 and 52.05 (2OCH3), 53.37
2
(d, JPC¼16.4 Hz, P–C–C H), 106.65 (CH), 109.81 (C–
1
3.1.7. Dimethyl 2-(2-pyridylamino)-3-(triphenylphos-
phoranylidene)butanedioate 2g. Pale yellow crystals, mp
196–1988C, 0.98 g, yield 98%. IR (KBr) (nmax/cm21): 3370
(NH), 1730 and 1608 (CvO). MS, m/z (%): 498 (Mþ, 4),
439 (100), 407 (40), 354 (10), 303 (15), 262 (55), 183 (34),
Br), 126.33 (d, JPC¼92.8 Hz, Cipso), 128.65 (d,
2
3JPC¼12.2 Hz, Cm), 132.02 (Cp), 133.82 (d, JPC¼9.5 Hz,
Co), 138.95 and 147.75 (2CH), 156.28 (NvC–N), 170.25
2
3
and 174.50 (2d, JPC¼8.3 Hz and JPC¼12.9 Hz, 2CvO
ester). 31P NMR: d 23.48 (Ph3PvC).

7218
I. Yavari et al. / Tetrahedron 58 (2002) 7213–7219
3.2. General procedure for preparation of compounds
3a–h
ethyl acetate) (Lit.21 126–1278C), 0.42 g, yield 97%. IR
(KBr) (nmax/cm21): 1565, 1469, 1305, 1102, 818. MS, m/z
(%): 433 (Mþþ2, 86), 431 (Mþ, 90), 277 (100), 183 (49),
156 (45), 78 (20). Anal. Calcd for C24H19BrNP (432.30): C,
66.68; H, 4.43; N, 3.24. Found: C, 66.7; H, 4.4; N, 3.2%. 1H
NMR: d 6.65 (2H, d, J¼8.2 Hz, 2CH), 7.05 (2H, d,
3.2.1. N-Phenyltriphenyliminophosphorane 3a. The pro-
cess for the preparation of 3a is described as an example. A
mixture of 2a (0.50 g, 1 mmol) in p-xylene (10 mL) was
refluxed for 10 h. The solvent was removed under reduced
pressure. Dimethyl fumarate sublimated under reduced
pressure and the residue recrystallised from 1:1 hexane–
ethyl acetate as colorless crystals, mp 131–1338C (Lit.21
133–1348C), 0.34 g, yield 97%. IR (KBr) (nmax/cm21):
1577, 1473, 1328, 1103, 747, 711, 688, 563, 517. MS, m/z
(%): 353 (Mþ, 100), 277 (71), 183 (42), 78 (51). Anal. Calcd
for C24H20NP (353.40): C, 81.57; H, 5.70; N, 3.96. Found:
C, 81.6; H, 5.7; N, 4.0%. 1H NMR: d 6.64 (1H, t, J¼7.2 Hz,
CH), 6.80 (2H, d, J¼8.0 Hz, 2CH), 7.00 (2H, dd, J¼7.2,
8.0 Hz, 2CH), 7.42 (6H, td, 3JHH¼7.7 Hz and 4JPH¼2.9 Hz,
3
J¼8.2 Hz, 2CH), 7.42 (6H, dt, JHH¼7.7 Hz and
3
4JPH¼3.0 Hz, 6metaCH), 7.49 (3H, dt, JHH¼7.7 Hz and
3
5JPH¼1.3 Hz, 3paraCH), 7.72 (6H, dd, JHH¼7.7 Hz and
3JPH¼11.6 Hz, 6orthoCH). 13C NMR: d 109.27 (C–Br),
3
3
124.94 (d, JPC¼17.6 Hz, CH), 128.63 (d, JPC¼12.1 Hz,
Cm), 130.56 (d, JPC¼99.4 Hz, Cipso), 131.28 (CH), 131.78
1
(d, JPC¼1.8 Hz, Cp), 132.48 (d, JPC¼9.6 Hz, Co), 150.45
4
2
(d, 2JPC¼1.9 Hz, C–NvP). 31P NMR: d 4.22 (Ph3PvN).
3.2.5. N-(4-Nitrophenyl)triphenyliminophosphorane 3e.
Pale yellow crystals, mp 155–1578C (from ether) (Lit.21
158–1598C), 0.39 g, yield 98%. IR (KBr) (nmax/cm21):
1570, 1488, 1378, 1209, 1099. MS, m/z (%): 398 (Mþ, 100),
351 (25), 321 (8), 277 (30), 262 (20), 183 (85), 152 (20), 108
(30), 77 (25). Anal. Calcd for C24H19N2O2P (398.40): C,
72.36; H, 4.81; N, 7.03. Found: C, 72.4; H, 4.7; N, 7.0%. 1H
3
5
6metaCH), 7.49 (3H, dt, JHH¼7.7 Hz and JPH¼1.5 Hz,
3para CH), 7.74 (6H, dd, 3JHH¼7.7 Hz and 3JPH¼12.0 Hz,
6orthoCH). 13C NMR: d 117.31 (CH), 123.46 (d,
3
3JPC¼17.5 Hz, CH), 128.55 (d, JPC¼12.2 Hz, Cm),
1
128.58 (CH), 131.15 (d, JPC¼98.9 Hz, Cipso), 131.61 (d,
2
3
4JPC¼2.6 Hz, Cp), 132.61 (d, JPC¼9.6 Hz, Co), 151.12 (d,
NMR: d 6.68 (2H, d, JHH¼9.2 Hz, 2CH), 7.48 (6H, td,
2JPC¼2.1 Hz, C–NvP). 31P NMR: d 3.11 (Ph3PvN).
3JHH¼7.6 Hz and JPH¼3.0 Hz, 6metaCH), 7.57 (3H, dt,
4
5
3JHH¼7.6 Hz and JPH¼1.4 Hz, 3paraCH), 7.73 (6H, dd,
3
3.2.2.N-1-Naphthyltriphenyliminophosphorane 3b. Color-
less crystals, mp 110–1128C (from 1:1 hexane–ethyl acetate),
0.40 g, yield 98%. IR (KBr) (nmax/cm21): 1555, 1443, 1392,
1323, 1115, 711, 519. MS, m/z (%): 403 (Mþ, 100), 277 (84),
183 (25), 128 (28), 78 (20). Anal. Calcd for C28H22NP
(403.46): C, 83.36; H, 5.50; N, 3.47. Found: C, 83.4; H, 5.6; N,
3JHH¼7.6 Hz and JPH¼12.2 Hz, 6orthoCH), 7.90 (2H, d,
3JHH¼9.2 Hz, 2CH). 13C NMR: d 122.20 (d, 3JPC¼19.0 Hz,
3
CH), 125.50 (CH), 128.83 (d, JPC¼12.1 Hz, Cm), 129.13
1
4
(d, JPC¼100.0 Hz, Cipso), 132.14 (d, JPC¼2.9 Hz, Cp),
132.56 (d, JPC¼9.7 Hz, Co), 137.97 (C), 160.05 (d,
2
2JPC¼2.5 Hz, C–NvP). 31P NMR: d 7.72 (Ph3PvN).
1
3.5%. H NMR: d 6.43 (1H, d, J¼7.4 Hz, CH), 6.99 (1H, t,
J¼7.8 Hz, CH), 7.13 (1H, d, J¼8.1 Hz, CH), 7.42 (7H, m,
6metaCH and CH), 7.49 (4H, m, 3paraCH and CH), 7.71 (1H,
3.2.6. N-(4-Acetylphenyl)triphenyliminophosphorane 3f.
Colorless crystals, mp 127–1308C (from ether), 0.38 g,
yield 97%. IR (KBr) (nmax/cm21): 1646, 1577, 1494, 1347,
1263, 1173, 1102. MS, m/z (%): 395 (Mþ, 45), 380 (8), 277
(100), 183 (25), 152 (10), 135 (40), 120 (80), 92 (50), 77
(30). Anal. Calcd for C26H22NOP (395.44): C, 78.97; H,
5.61; N, 3.54. Found: C, 78.8; H, 5.6; N, 3.5%. 1H NMR: d
3
d, J¼7.8 Hz, CH), 7.83 (6H, dd, JHH¼8.0 Hz and
3JPH¼11.9 Hz, 6orthoCH), 8.91 (1H, d, J¼8.1 Hz, CH). 13
C
3
NMR: d 114.12 (d, JPC¼10.6 Hz, CH), 116.70, 123.73,
125.44, 125.46, 126.23 and 127.40 (6CH), 128.60 (d,
3JPC¼12.2 Hz, Cm), 131.17 (d, 1JPC¼99.6 Hz, Cipso), 131.66
(d, 4JPC¼2.6 Hz, Cp), 131.98 (d, 3JPC¼22.1 Hz, C), 132.64 (d,
3
2.45 (3H, s, CH3), 6.76 (2H, d, JHH¼8.7 Hz, 2CH), 7.47
4
3
4
2JPC¼9.6 Hz, Co), 135.06 (d, JPC¼2.6 Hz, C), 148.01
(6H, dt, JHH¼7.6 Hz and JPH¼3.0 Hz, 6metaCH), 7.55
(C–NvP). 31P NMR: d 3.45 (Ph3PvN).
(3H, dt, JHH¼7.6 Hz and JPH¼1.4 Hz, 3paraCH), 7.67
3
5
3
(2H, d, J¼8.7 Hz, 2CH), 7.67 (6H, dd, JHH¼7.6 Hz and
3.2.3. N-(4-Methylphenyl)triphenyliminophosphorane
3c. Colorless crystals, mp 137–1398C (from 1:1 hexane–
ethyl acetate) (Lit.21 136–1378C), 0.36 g, yield 98%. IR
(KBr) (nmax/cm21): 1595, 1494, 1426, 1323, 1103, 813,
711, 518. MS, m/z (%): 367 (Mþ, 100), 277 (62), 183 (45),
91 (18), 78 (33). Anal. Calcd for C25H22NP (367.43): C,
81.72; H, 6.04; N, 3.81. Found: C, 81.7; H, 6.0; N, 3.8%. 1H
NMR: d 2.15 (3H, s, CH3), 6.73 (2H, d, J¼8.0 Hz, 2CH),
3JPH¼12.2 Hz, 6orthoCH). 13C NMR: d 25.98 (CH3),
3
122.62 (d, JPC¼18.9 Hz, CH), 126.75 (C), 128.83 (d,
3JPC¼12.2 Hz, Cm), 129.98 (d, JPC¼1.6 Hz, CH), 130.01
4
(d, JPC¼99.8 Hz, Cipso), 132.09 (d, JPC¼2.9 Hz, Cp),
1
4
132.56 (d, JPC¼9.7 Hz, Co), 157.67 (d, JPC¼2.4 Hz,
2
2
C–NvP), 196.63 (CvO). 31P NMR: d 6.53 (Ph3PvN).
3.2.7. N-(2-Pyridyl)triphenyliminophosphorane 3g. Color-
less crystals, mp 146–1488C (from ether), 0.35 g, yield 98%.
IR (KBr) (nmax/cm21): 1574, 1452, 1418, 1337, 1104, 1011.
MS, m/z (%): 354 (Mþ, 100), 277 (70), 199 (10), 183 (50), 152
(8), 94 (15), 77 (25). Anal. Calcd for C23H19N2P (354.39): C,
77.95; H, 5.40; N, 7.90. Found: C, 78.1; H, 5.4; N, 7.8%. 1H
NMR: d 6.47 (1H, dd, J¼7.0, 5.1 Hz, CH), 7.01 (1H, d,
J¼8.3 Hz, CH), 7.39 (1H, dt, 3JHH¼7.1 Hz and 4JHH¼1.1 Hz,
3
6.80 (2H, d, J¼8.0 Hz, 2CH), 7.36 (6H, dt, JHH¼7.9 Hz
4
3
and JPH¼2.9 Hz, 6metaCH), 7.43 (3H, dt, JHH¼7.9 Hz
5
3
and JPH¼1.3 Hz, 3paraCH), 7.73 (6H, dd, JHH¼7.9 Hz
3
and JPH¼11.7 Hz, 6orthoCH). 13C NMR: d 20.49 (CH3),
123.17 (d, 3JPC¼17.4 Hz, CH), 126.19 (C–CH3), 128.48 (d,
3JPC¼11.9 Hz, Cm), 129.20 (CH), 131.20 (d, 1JPC¼98.6 Hz,
C
ipso), 131.52 (d, 4JPC¼2.5 Hz, Cp), 132.54 (d,
2JPC¼9.6 Hz, Co), 148.30 (d, JPC¼2.6 Hz, C–NvP). 31P
CH), 7.43 (6H, dt, JHH¼7.6 and JPH¼3.0 Hz, 6metaCH),
7.50 (3H, dt, 3JHH¼7.6 Hz and 5JPH¼1.4 Hz, 3paraCH), 7.86
2
3
4
NMR: d 3.02 (Ph3PvN).
3
3
(1H, d, JHH¼7.0 Hz, CH), 7.89 (6H, dd, JHH¼7.6 Hz and
3JPH¼12.2 Hz, 6orthoCH). 13C NMR: d 112.5 (CH), 117.16
(d, 3JPC¼24.0 Hz, CH), 128.83(d, 3JPC¼12.0 Hz, Cm), 130.34
3.2.4. N-(4-Bromophenyl)triphenyliminophosphorane
3d. Colorless crystals, mp 125–1268C (from 1:1 hexane–

I. Yavari et al. / Tetrahedron 58 (2002) 7213–7219
7219
(d, 1JPC¼99.6 Hz, Cipso), 131.36 (d, 4JPC¼2.6 Hz, Cp), 133.05
References
2
4
(d, JPC¼9.6 Hz, Co), 136.50 (d, JPC¼4.5 Hz, CH), 146.95
(CH), 163.62 (d, 2JPC¼6.3 Hz, C–NvP). 31P NMR: d 14.25
(Ph3PvN).
1. Johnson, A. W. Ylides and Imines of Phosphorus. Wiley: New
York, 1993.
2. Johnson, A. W. Ylid Chemistry. Academic: New York, 1966.
3. Golobolov, Y. G.; Kasuchin, L. F. Tetrahedron 1992, 48,
1353.
3.2.8. N-(5-Bromo-2-pyridyl)triphenyliminophosphor-
ane 3h. Colorless crystals, mp 165–1678C (from 1:1
hexane–ethyl acetate), 0.42 g, yield 98%. IR (KBr) (nmax
/
4. Gusar, N. I. Russ. Chem. Rev. 1991, 60, 146.
5. Dehnicke, K.; Strable, J. Polyhedron 1989, 8, 707.
6. Staudinger, H.; Meyer, J. Helv. Chim. Acta 1919, 2, 635.
7. Abel, S. W.; Mucklejohn, S. A. Phosphorus, Sulfur, Silicon
1981, 9, 235.
cm21): 1559, 1445, 1365, 1314, 1105, 1004. MS, m/z (%):
434 (Mþþ2, 95), 432 (Mþ, 100), 277 (66), 199 (15), 183
(33), 152 (20), 78 (40). Anal. Calcd for C23H18BrN2P
(433.29): C, 63.76; H, 4.19; N, 6.47. Found: C, 63.7; H, 4.2;
N, 6.5%. 1H NMR: d 6.82 (1H, d, J¼8.7 Hz, CH), 7.34 (1H,
8. Alkock, H. R. Phosphorus–nitrogen Compounds. Academic:
New York, 1972.
3
4
dd, JHH¼8.7 Hz and JHH¼2.1 Hz, CH), 7.38 (6H, td,
3JHH¼8.0 Hz and JPH¼2.3 Hz, 6metaCH), 7.44 (3H, t,
9. Scriven, E. S. V.; Turnbull, K. Chem. Rev. 1988, 88, 298.
10. Neilson, R. H.; Wisian-Nielson, P. Chem. Rev. 1988, 88, 541.
11. Hughes, A. N. Heterocycles 1981, 15, 637. and references
therein.
4
3JHH¼7.5 Hz, 3paraCH), 7.78 (6H, dd, JHH¼8.0 Hz and
3
3JPH¼12.0 Hz, 6orthoCH), 7.80 (1H, d, 4JHH¼2.1 Hz, CH).
13C NMR: d 107.24 (C–Br), 118.99 (d, 3JPC¼24.0 Hz, CH),
128.28 (d, JPC¼12.0 Hz, Cm), 129.81 (d, JPC¼99.9 Hz,
12. Shaw, M. A.; Ward, R. S. Top. Phosphorus Chem. 1972, 7, 1.
13. Zbiral, E. Synthesis 1974, 775.
3
1
C
ipso), 131.55 (d, 4JPC¼2.6 Hz, Cp), 133.02 (d,
2JPC¼9.7 Hz, Co), 138.91 (d, JPC¼4.5 Hz, CH), 147.43
14. Becker, K. B. Tetrahedron 1980, 36, 1717.
15. Ferrer, P.; Avendo, C.; Sollhubor, M. Liebigs Ann. Chem.
1995, 1895.
4
(CH), 162.44 (d, JPC¼6.5 Hz, C–NvP). 31P NMR: d
2
14.62 (Ph3PvN).
16. Kolodiazhynyi, O. I. Russ. Chem. Rev. 1997, 66, 225.
17. Pietrusiewiz, K. M.; Zablocka, M. Chem. Rev. 1983, 83, 109.
18. Bestmann, H. J.; Vostrowsky, O. Top. Curr. Chem. 1983, 109,
85.
Acknowledgments
19. Bestmann, H. J.; Zimmermann, R. Top. Curr. Chem. 1970, 20,
88.
This research was supported by the National
Research Council of the Islamic Republic of Iran (NRCI)
as a National Research project under the grant number
989.
20. Fox, B. A.; Threlfall, T. L. Organic Syntheses, Wiley: New
York, 1973; Collect. Vol. 5. p 346.
21. Johnson, A. W.; Wong, S. C. K. Can. J. Chem. 1966, 44, 2793.