A facile and expedient one-pot three-component reaction leading to multifunctionalized stabilized phosphorus ylides

Article abstract of DOI:10.1007/s12039-012-0293-6

A three-component reaction between triphenylphosphine, a dialkyl acetylenedicarboxylate and phthalazin-1(2H)-ones that affords novel organic phosphorane derivatives in good to excellent yields is reported. FTIR, ¹H, ¹³C and ³¹P NMR and elemental analyses have been utilized to characterize the synthesized compounds. Indian Academy of Sciences.

Full text of DOI:10.1007/s12039-012-0293-6

c
J. Chem. Sci. Vol. 124, No. 5, September 2012, pp. 1007–1012. ꢀ Indian Academy of Sciences.
A facile and expedient one-pot three-component reaction leading
to multifunctionalized stabilized phosphorus ylides
ZAHRA HASSANI∗ and ZEINAB ESFANDIARPOUR
Department of New Materials, International Center for Science, High Technology & Environmental Sciences,
Kerman, 7631133131, Iran
e-mail: hassani_za@icst.ac.ir; hassanizahra@yahoo.com
MS received 14 August 2011; revised 17 March 2012; accepted 20 April 2012
Abstract. A three-component reaction between triphenylphosphine, a dialkyl acetylenedicarboxylate and
phthalazin-1(2H)-ones that affords novel organic phosphorane derivatives in good to excellent yields is
reported. FTIR, 1H, 13C and 31P NMR and elemental analyses have been utilized to characterize the synthesized
compounds.
Keywords. Phosphoranes; acetylenic esters; heterocyclic compounds; phthalazin-1(2H)-one;
three-component reaction.
1. Introduction
2. Experimental
Phthalazin-1(2H)-one and their analogues represent 2.1 General procedures
an important class of nitrogen-containing heterocyclic
1
compounds which exhibit useful biological activi- The H and 13C NMR spectra were acquired from
ties. Particularly, in recent years, stilbene-related het- a BRUKER DRX-500 AVANCE NMR spectrometer
erocyclic compounds comprising of benzalphthalide, (using SiMe4 as the internal standard). 31P NMR spec-
phthalazinone, imidazoindole and pyrimidoisoindole tra was recorded on a Bruker Avance DRX instru-
derivatives have been tested for their anti-HIV activi- ment at 162.0 MHz. Infrared absorption spectra were
ty.1 Some phthalazin-1-ones and their derivatives obtained from 4000 to 400 cm−1 in KBr pellet using a
have shown pharmacological utility as vasorelaxant,2 MATTSON 1000 FT-IR spectrometer. Elemental analy-
polymerase inhibitors,3 anxiolytics4 and antiprotozoal ses were performed using Heracus CHN-O-Rapid ana-
potency.5,6 recently, one-pot multicomponent reactions lyzer. Melting points were determined on an Electro-
have emerged as a forceful tool in synthetic organic thermal 9200 apparatus and are uncorrected.
chemistry due to their significant advantages.7,8 A prac-
All chemicals were purchased from Merck or Fluka
tical and expedient construction of highly functiona- and Sigma-Aldrich Chemical Companies. All common
lized and diversified molecules from simple starting reagents and solvents were used as obtained from com-
materials is highly desirable and is considered as a great mercial suppliers without further purification. Benzal-
challenge.
phthalide was prepared from phthalic anhydride and
In recent years, as part of our studies on the develop- phenylacetic acid in the presence of sodium acetate
ment of useful and beneficial methods for the prepara- following a protocol mentioned in the literature.1–6,21
tion of organic compounds, we have been interested in Phthalazin-1(2H)-one was prepared by us through con-
the synthesis of organophosphorus compounds;9 that is, densation of benzalphthalides with hydrazines under
those bearing a carbon atom bound directly to a phos- reflux according to a method used by other reserch-
phorus atom. This interest is due to usefullness of such ers.1–6,22
compounds in a variety of biological, industrial and
Dimethyl acetylenedicarboxylate (0.12 mL, 1 mmol)
was added drop-wise to a magnetically stirred solution
of triphenylphosphine (0.26 g, 1 mmol) and Phthalazin-
1(2H)-one (0.24 g, 1 mmol) in 20 mL of acetone as
a solvent. After the addition was complete (approxi-
mately 5 min), the mixture was stirred for an addi-
tional 3 h at ambient temperature before being filtered.
synthetic applications.10–13
∗For correspondence
1007

1008
Zahra Hassani and Zeinab Esfandiarpour
The collected solids were washed thoroughly with ace- 131.76 (Cpara)*, 132.29 (CH), 132.40 (C), 133.81 (d,
tone yielding a white powder.
2 JPC = 10.1 Hz, Cortho), 138.62 (C), 143.04 (C), 158.86
2
(C=O), 170.93 (d, JPC = 11.3 Hz, C=O), 171.56
(C=O) ppm. 31P NMR (162.0 MHz, CDCl3): δ =
2.1a Dimethyl 2-[4-benzyl-1-oxo-2(1H)phthalazinyl]-
3-(1,1,1-triphenyl-λ5-phosphanylidene) succinate (5a):
(White powder, 0.60 g, m.p 116–118◦C, yield 93%);
IR (KBr) (νmax, cm−1): 1753, 1651 and 1612 (C=O).
Anal. Calcd. For C39H33N2O5P (640.66): C, 73.11; H,
5.19; N, 4.37%. Found: C, 73.23; H, 5.09; N, 4.28%.
1
23.00 ppm. Isomer, (Z) (48%) H NMR (500 MHz,
3
CDCl3): δ = 0.48 (3H, t, JH H = 5.0 Hz, CH3), 1.22
3
3
(3H, t, JH H = 5.0 Hz, CH3), 6.39 (1H, d, JP H
=
20.0 Hz, P=C–CH) ppm. 13C NMR (125 MHz, CDCl3):
δ = 14.12 and 14.96 (2 CH3), 39.21 (CH2), 39.28 (d,
1 JPC = 132.0 Hz, P=C), 58.37 and 60.90 (2 OCH2),
1
Isomer, (E) (55%) H NMR (500 MHz, CDCl3): δ =
2
61.18 (d, JPC = 13.8 Hz, P=C–CH), 126.37 (CH),
3.55 and 3.61 (6H, 2s, 2 OCH3), 4.29 (2H, s, CH2), 6.34
127.66 (d, 1 JPC = 91.8 Hz, Cipso), 127.40 (CH), 128.40
3
(1H, d, JP H = 20.0 Hz, P=C–CH), 7.20–8.34 (48H,
(d, JPC = 11.3 Hz, Cmeta), 129.49 (CH), 133.97 (d,
3
m, arom)*ppm. 13C NMR (125 MHz, CDCl3): δ =
39.05 (CH2), 40.86 (d, 1 JPC = 139.6 Hz, P=C)*, 50.38
and 52.16 (2 OCH3), 61.28 (d, 2 JPC = 13.8 Hz, P=C–
CH), 124.95 (CH)*, 127.34 (d, 1 JPC = 83.0 Hz, Cipso),
126.52 (CH), 127.33 (CH)*, 128.19 (C), 128.32 (CH),
2 JPC = 10.1 Hz, Cortho), 138.78 (C), 142.96 (C), 158.82
2
(C=O), 170.87 (d, JPC = 11.3 Hz, C=O), 171.42
(C=O) ppm. 31P NMR (162.0 MHz, CDCl3): δ =
23.06 ppm.
3
128.50 (CH)*, 128.64 (d, JPC = 11.3 Hz, Cmeta)*,
129.46 (CH)*, 130.55 (CH), 131.90 (Cpara)*, 132.57
2.1c Dimethyl 2-[4-(4-methoxybenzyl-1-oxo-2(1H) phtha-
lazinyl]-3-(1,1,1-triphenyl-λ5-phosphanylidene) succinate
(5c): (White powder, 0.55 g, m.p 124–126◦C, yield
82%); IR (KBr) (νmax, cm−1): 1753, 1651 and 1625
(C=O). Anal. Calcd. For C40H35N2O5P (670.69): C,
71.63; H, 5.26; N, 4.18%. Found: C, 71.69; H, 5.16;
N, 4.08%. Isomer, (E) (58%) (1H NMR (500 MHz,
CDCl3): δ = 3.56 and 3.59 (6H, 2s, 2 OCH3), 3.79
2
(C), 133.90 (d, JPC = 6.3 Hz, Cortho), 138.49 (C),
143.31 (C), 158.93 (C=O), 171.49 (d, 2 JPC = 12.6 Hz,
3
C=O), 171.49 (d, JPC = 7.5 Hz, C=O)* ppm.31P
NMR (162.0 MHz, CDCl3): δ = 22.80 ppm. Isomer,
1
(Z) (45%) H NMR (500 MHz, CDCl3): δ = 3.15 and
3.60 (6H, 2s, 2 OCH3), 4.32 (2H, s, CH2), 6.26 (1H, d,
3 JP H = 20.0 Hz, P=C–CH) ppm. 13C NMR (125 MHz,
CDCl3): δ = 39.11 (CH2), 49.10 and 52.27 (2 OCH3),
(3H, s, OCH3), 4.25 (2H, s, CH2), 6.29 (1H, d, 3 JP H
=
61.08 (d, 2 JPC = 15.1 Hz, P=C–CH), 126.60 (d, 1 JPC
=
20.0 Hz, P=C–CH), 6.80–8.35 (46H, m, arom)* ppm.
13C NMR (125 MHz, CDCl3): δ = 38.26 (CH2), 40.84
84.3 Hz, Cipso), 126.43 (CH), 128.26 (C), 128.43 (CH),
2
130.47 (CH), 132.43 (C), 133.82 (d, JPC = 6.3 Hz,
1
(d, JPC = 139.4 Hz, P=C)*, 50.36 and 52.13 (2
Cortho), 138.66 (C), 143.26 (C), 158.99 (C=O), 170.06
(d, 2 JPC = 12.6 Hz, C=O) ppm. 31P NMR (162.0 MHz,
CDCl3): δ = 23.00 ppm.
2
OCH3), 55.27 (2 OCH3)*, 61.24 (d, JPC = 14.6 Hz,
P=C–CH), 114.12 (CH), 124.95 (CH)*, 126.73 (d,
1 JPC = 92.2 Hz, Cipso), 127.36 (CH)*, 128.27 (C),
3
128.63 (d, JPC = 12.1 Hz, Cmeta), 129.28 (CH)*,
129.42 (CH), 130.36 (C), 130.54 (C), 131.34 (d, 4 JPC
=
2.1b Diethyl 2-[4-benzyl-1-oxo-2(1H)phthalazinyl]-
3-(1,1,1-triphenyl-λ5-phosphanylidene) succinate (5b):
(White powder, 0.61 g, m.p 200–202◦C, yield
91%) IR (KBr) (νmax, cm−1): 1753, 1651 and 1610
(C=O). Anal. Calcd. For C41H37N2O5P (668.72): C,
73.64; H, 5.58; N, 4.19%. Found: C, 73.70; H, 5.47; N,
4.26%. Isomer, (E) (52%) 1H NMR (500 MHz, CDCl3):
2.5 Hz, Cpara)*, 132.46 (CH), 133.90 (d, 2 JPC = 9.8 Hz,
Cortho), 143.54 (C), 158.28 (C), 158.96 (C=O), 171.48
(d, 2 JPC = 11.2 Hz, C=O), 171.61 (d, 3 JPC = 6.1 Hz,
C=O) ppm. 31P NMR (162.0 MHz, CDCl3): δ =
1
22.70 ppm. Isomer, (Z) (42%) H NMR (500 MHz,
CDCl3): δ = 3.14 and 3.59 (6H, 2s, 2 OCH3), 3.78
(3H, s, OCH3), 4.21 (2H, s, CH2), 6.22 (1H, d, 3 JP H
=
3
δ = 1.17 (3H, t, JH H = 5.0 Hz, CH3), 1.28 (3H, t,
20.0 Hz, P=C–CH) ppm.13C NMR (125 MHz, CDCl3):
3 JH H = 5.0 Hz, CH3), 3.70–4.17 (8H, m, 4 OCH2)*,
2
δ = 38.30 (CH2), 49.04 and 52.25 (2 OCH3), 62.07
4.326 (2H, s, CH2), 4.36 (2H, d, JH H = 15.0 Hz,
2
3
(d, JPC = 14.4 Hz, P=C–CH), 114.22 (CH), 127.41
CH2)*, 6.02 (1H, d, JP H = 20.0 Hz, P=C–CH),
1
(d, JPC = 91.9 Hz, Cipso), 128.33 (C), 128.53 (d,
7.21–8.35 (48H, m, arom)*ppm. 13C NMR (125 MHz,
3 JPC = 11.9 Hz, Cmeta), 129.46 (CH), 130.44 (C),
CDCl3): δ = 13.96 and 14.05 (2 CH3), 39.06 (CH2),
2
1
130.71 (C), 132.32 (CH), 133.86 (d, JPC = 9.6 Hz,
40.76 (d, JPC = 139.6 Hz, P=C), 57.64 and 60.89
Cortho), 143.45(C), 158.22 (C), 158.90 (C=O), 169.97
(d, 2 JPC = 11.2 Hz, C=O), 171.75 (d, 3 JPC = 6.1 Hz,
C=O) ppm. 31P NMR (162.0 MHz, CDCl3): δ =
23.09 ppm.
(2 OCH2), 61.16 (d, 2 JPC = 15.1 Hz, P=C–CH), 124.85
(CH)*, 126.48 (CH), 126.92 (d, 1 JPC = 93.1 Hz, Cipso),
127.34 (CH), 128.25 (C)*, 128.42 (CH)*, 128.59 (d,
3 JPC = 11.3 Hz, Cmeta), 129.45 (CH), 130.35 (CH)*,

A facile one-pot three-component reaction leading to phosphorus ylides
1009
2.1d Diethyl 2-[4-methoxybenzyl-1-oxo-2(1H) phthal- 129.268 (CH)*, 129.94 (CH), 130.64 (C), 131.93 (d,
azinyl]-3-(1,1,1-triphenyl-λ5-phosphanylidene) succinate 4 JPC = 2.3 Hz, Cpara)*, 132.37 (C), 132.60 (CH),
2
(5d): (White powder, 0.56 g, m.p 100–103◦C, yield 133.85 (d, JPC = 9.3 Hz, Cortho), 136.59 (C), 142.78
80%) IR (KBr) (νmax, cm−1): 1753, 1651 and 1625 (C), 158.87 (C=O), 171.44 (d, 2 JPC = 11.5 Hz, C=O),
(C=O). Anal. Calcd. For C42H39N2O6P (698.74): C, 171.58 (C=O) ppm. 31P NMR (162.0 MHz, CDCl3):
72.19; H, 5.63; N, 4.01%. Found: C, 72.22; H, 5.56; N, δ = 22.79 ppm. Isomer, (Z) (40%) 1H NMR (500 MHz,
3.95%. Isomer, (Z) (60%) 1H NMR (500 MHz, CDCl3): CDCl3): δ = 3.14 and 3.59 (6H, 2s, 2 OCH3), 4.25
3
3
δ = 0.47 (3H, t, JH H = 7.1 Hz, CH3), 1.17 (3H, (2H, s, CH2), 6.19 (1H, d, JP H = 22.0 Hz, P=C–
t, JH H = 7.1 Hz, CH3), 3.78 (3H, s, OCH3), 3.69– CH) ppm. 13C NMR (125 MHz, CDCl3): δ = 38.91
3
1
4.08 (8H, m, 4 OCH2)*, 4.27 (2H, s, CH2), 6.01 (1H, (CH2), 39.44 (d, JPC = 131.6 Hz, P=C), 50.34 and
3
2
d, JP H = 23.5 Hz, P=C–CH), 6.80–8.46 (46H, m, 52.31 (2 OCH3), 62.07 (d, JPC = 14.8 Hz, P=C–
arom)*ppm. 13C NMR (125 MHz, CDCl3): δ = 13.96 CH), 124.58 (CH), 127.34 (d, JPC = 91.9 Hz, Cipso),
1
1
3
and 14.96 (2 CH3), 38.22 (CH2), 40.81 (d, JPC
=
128.29 (C), 128.75 (d, JPC = 12.3 Hz, Cmeta), 129.26
139.6 Hz, P=C), 55.26 and 57.66 (2 OCH2), 60.89 (CH), 130.55 (C), 132.26 (C), 132.47 (CH), 133.77 (d,
(2 OCH3)*, 61.13 (d, JPC = 15.6 Hz, P=C–CH), 2 JPC = 9.0 Hz, Cortho), 137.09 (C), 142.68 (C), 158.81
2
114.08 (CH), 124.86 (CH), 126.94 (d, 1 JPC = 92.8 Hz, (C=O), 169.90 (d, JPC = 12.5 Hz, C=O), 171.73
2
Cipso), 127.33 (CH), 128.41 (C), 128.42 (d, JPC
=
(C=O) ppm. 31P NMR (162.0 MHz, CDCl3): δ =
3
12.2 Hz, Cmeta), 129.32 (CH), 130.30 (CH), 130.65 (C), 23.10 ppm.
131.79 (Cpara)*, 132.36 (CH), 133.82 (d, 2 JPC = 9.8 Hz,
Cortho), 143.36 (C), 158.21 (C), 158.82 (C=O), 170.89
(d, JPC = 12.2 Hz, C=O), 171.45 (C=O) ppm. 31P
2
2.1f Diethyl 2-[4-chlorobenzyl-1-oxo-2(1H)phtha-
lazinyl]-3-(1,1,1-triphenyl-λ5-phosphanylidene) suc-
cinate (5f): (Pale yellow powder, 0.62 g, m.p 118–
120◦C, yield 88%) IR (KBr) (νmax, cm−1): 1753, 1651
and 1625 (C=O). Anal. Calcd. For C41H36ClN2O5P
(703.16): C, 70.03; H, 5.16; N, 3.98%. Found: C,
70.10; H, 5.10; N, 3.94%. Isomer, (E) (50%) 1H NMR
NMR (162.0 MHz, CDCl3): δ = 23.12 ppm. Isomer,
(E) (40%)1H NMR (500 MHz, CDCl3): δ = 0.91 (3H,
3
3
t, JH H = 7.1 Hz, CH3), 1.22 (3H, t, JH H = 7.1 Hz,
CH3), 3.79 (3H, s, OCH3), 4.30 (2H, s, CH2), 6.38
(1H, d, JP H = 23.5 Hz, P=C–CH) ppm. 13C NMR
3
(125 MHz, CDCl3): δ = 14.06 and 14.13 (2 CH3),
38.38 (CH2), 39.30 (d, 1 JPC = 135.5 Hz, P=C), 58.38
3
(500 MHz, CDCl3): δ = 1.59 (3H, t, JH H = 6.8 Hz,
and 60.39 (2 OCH2), 62.18 (d, 2 JPC = 14.4 Hz, P=C–
3
CH3), 1.23 (3H, t, JH H = 7.0 Hz, CH3), 4.34 (2H,
1
3
CH), 114.09 (CH), 124.90 (CH), 127.67 (d, JPC
=
s, CH2), 6.27 (1H, d, JP H = 20.0 Hz, P=C–CH),
92.1 Hz, Cipso), 127.39 (CH), 128.29 (C), 128.61 (d,
3 JPC = 12.3 Hz, Cmeta), 129.41 (CH), 129.47 (CH),
7.16–8.34 (46H, m, arom)*ppm. 13C NMR (125 MHz,
CDCl3): δ = 13.95 and 14.95 (2 CH3), 38.53 (CH2),
2
1
130.77 (C), 132.25 (CH), 133.98 (d, JPC = 9.8 Hz,
40.78 (d, JPC = 136.0 Hz, P=C), 57.67 and 60.95 (2
Cortho), 143.28 (C), 158.28 (C), 158.88 (C=O), 169.52
2
OCH2), 61.20 (d, JPC = 15.9 Hz, P=C–CH), 124.58
(d, JPC = 13.6 Hz, C=O), 171.59 (C=O) ppm. 31P
2
(CH), 126.87 (d, 1 JPC = 92.5 Hz, Cipso), 127.52 (CH),
128.44 (d, 3 JPC = 12.2 Hz, Cmeta), 128.73 (CH), 129.27
NMR (162.0 MHz, CDCl3): δ = 23.20 ppm.
(C), 129.72 (CH)*, 129.93 (CH)*, 130.48(C), 131.86
(Cpara)*, 132.36 (C), 133.39 (CH), 133.78 (d, JPC
=
2
2.1e Dimethyl 2-[4-(4-chlorobenzyl-1-oxo-2(1H) phthal- 9.7 Hz, Cortho), 137.10 (C), 142.50 (C), 158.75 (C=O),
azinyl]-3-(1,1,1-triphenyl-λ5-phosphanylidene) succinate 170.84 (d, JPC = 12.5 Hz, C=O), 170.91 (d, JPC
=
2
3
(5e): (Pale yellow powder, 0.66 g, m.p 138–140◦C, 10.6 Hz, C=O) ppm. 31P NMR (162.0 MHz, CDCl3): δ
yield 98%); IR (KBr) (νmax, cm−1): 1753, 1651 = 23.10 ppm. Isomer, (Z) (50%) H NMR (500 MHz,
1
3
and 1625 (C=O). Anal. Calcd. For C39H32ClN2O5P CDCl3): δ = 0.47 (3H, t, JH H = 7.0 Hz, CH3), 1.29
3
(675.11): C, 69.38; H, 4.78; N, 4.15%. Found: C, (3H, t, JH H = 7.0 Hz, CH3), 3.99–4.08 (8H, m, 4
1
3
69.41; H, 4.71; N, 4.08%. Isomer, (E) (60%) HNMR OCH2)*, 4.30 (2H, s, CH2), 5.95 (1H, d, JP H
=
(500 MHz, CDCl3): δ = 3.58 and 3.60 (6H, 2s, 2 20.0 Hz, P=C–CH) ppm. 13C NMR (125 MHz, CDCl3):
OCH3), 4.28 (2H, s, CH2), 6.15 (1H, d, 3 JP H = 22.0 Hz, δ = 14.10 and 14.14 (2 CH3), 38.36 (CH2), 39.17 (d,
P=C–CH), 7.16–8.35 (46H, m, arom)*ppm. 13C NMR 1 JPC = 136.7 Hz, P=C), 58.36 and 60.94 (2 OCH2),
1
2
(125 MHz, CDCl3): δ = 38.40 (CH2), 40.81 (d, JPC 62.13 (d, JPC = 14.7 Hz, P=C–CH), 124.51 (CH),
= 139.3 Hz, P=C), 49.04 and 52.17 (2 OCH3), 61.31 127.61 (d, 1 JPC = 92.4 Hz, Cipso), 127.48 (CH), 128.63
(d, JPC = 14.7 Hz, P=C–CH), 124.63 (CH), 126.66 (d, JPC = 12.3 Hz, Cmeta), 128.78 (CH), 129.27 (C),
2
3
(d, JPC = 92.1 Hz, Cipso), 127.49 (CH)*, 128.25 130.51 (C), 132.24 (C), 132.50 (CH), 133.89 (d, 2 JPC
=
1
(C), 128.56 (d, JPC = 12.0 Hz, Cmeta), 129.74 (CH), 9.7 Hz, Cortho), 137.16 (C), 142.61 (C), 158.75 (C=O),
3

1010
Zahra Hassani and Zeinab Esfandiarpour
169.45 (d, 2 JPC = 12.4 Hz, C=O), 171.40 (C=O) ppm. 124.60 (CH), 126.90 (d, 1 JPC = 92.0 Hz, Cipso), 127.44
3
31P NMR (162.0 MHz, CDCl3): δ = 23.16 ppm.
(CH), 128.29 (C)*, 128.45 (d, JPC = 12.1 Hz, Cmeta),
3
129.27 (C), 129.81 (d, JC F = 7.9 Hz, CH), 130.43
(CH), 131.86 (Cpara)*, 132.36 (CH), 133.79 (d, 2 JPC
=
2.1g Dimethyl 2-[4-(4-fluorobenzyl-1-oxo-2(1H) phtha-
lazinyl]-3-(1,1,1-triphenyl-λ5-phosphanylidene) suc-
cinate (5g): (White powder, 0.57 g, m.p 194–196◦C,
yield 86%); IR (KBr) (νmax, cm−1): 1753, 1651
and 1600 (C=O). Anal. Calcd. For C39H32FN2O5P
(658.65): C, 71.12; H, 4.90; N, 4.25%. Found: C,
9.9 Hz, Cortho), 134.33 (d, JC F = 2.9 Hz, C), 142.78
4
1
(C), 158.86 (d, JC F = 8.5 Hz, C)*, 160.66 (C=O),
171.46 (d, 2 JPC = 11.3 Hz, C=O), 171.59 (C=O) ppm.
31P NMR (162.0 MHz, CDCl3): δ = 23.08 ppm. Isomer,
(Z) (50%) 1H NMR (500 MHz, CDCl3): δ = 0.47 (3H,
3
3
t, JH H = 7.1 Hz, CH3), 1.23 (3H, t, JH H = 7.1 Hz,
CH3), 3.69–4.32 (8H, m, 4 OCH2)*, 4.31 (2H, s, CH2),
5.94 (1H, d, 3 JP H = 20.9 Hz, P=C–CH) ppm. 13C NMR
(125 MHz, CDCl3): δ = 13.97 and 14.95 (2 CH3), 38.37
1
71.16; H, 4.84; N, 4.19%. Isomer, (E) (57%) HNMR
(500 MHz, CDCl3): δ = 3.58 and 3.60 (6H, 2s, 2
OCH3), 4.29 (2H, s, CH2), 6.21 (1H, d, 3 JP H = 20.9 Hz,
P=C–CH), 6.93–8.32 (46H, m, arom)*ppm. 13C NMR
1
(CH2), 39.35 (d, JPC = 133.3 Hz, P=C), 58.36 and
(125 MHz, CDCl3): δ = 38.26 (CH2), 40.36 (d, 1 JPC
=
60.93 (2 OCH2), 62.18 (d, 2 JPC = 14.6 Hz, P=C–CH),
90.5 Hz, P=C), 50.34 and 52.16 (2 OCH3), 61.28 (d,
2
115.52 (d, JC F = 5.8 Hz, CH), 124.67 (CH), 127.48
2 JPC = 14.7 Hz, P=C–CH), 115.37 (d, 2 JC F = 7.5 Hz,
(CH), 127.64 (d, JPC = 92.2 Hz, Cipso), 128.63 (d,
1
1
CH), 124.71 (CH), 126.68 (d, JPC = 92.0 Hz, Cipso),
3 JPC = 12.2 Hz, Cmeta), 129.31 (C), 129.98 (d, JC F
3
127.46 (CH)*, 128.28 (C), 128.66 (d, 3 JPC = 12.1 Hz,
= 7.7 Hz, CH), 130.42 (CH), 132.48 (CH), 133.92 (d,
3
Cmeta), 129.30 (C)*, 129.76 (d, JC F = 7.8 Hz, CH),
2 JPC = 9.8 Hz, Cortho), 134.26 (d, JC F = 2.9 Hz, C),
4
131.92 (d, 4 JPC = 2.0 Hz, Cpara)*, 132.56 (CH), 133.86
142.88 (C), 162.57 (C=O), 169.91 (d, 2 JPC = 12.5 Hz,
C=O), 171.73 (C=O) ppm. 31P NMR (162.0 MHz,
CDCl3): δ = 23.16 ppm.
2
4
(d, JPC = 9.0 Hz, Cortho), 134.14 (d, JC F = 2.8 Hz,
C), 143.05 (C), 158.85 (d, 1 JC F = 8.5 Hz, C)*, 160.66
2
(C=O), 171.40 (d, JPC = 12.5 Hz, C=O), 171.59
(C=O) ppm. 31P NMR (162.0 MHz, CDCl3): δ =
1
23.18 ppm. Isomer, (Z) (43%) H NMR (500 MHz,
3. Results and discussion
CDCl3): δ = 3.15 and 3.59 (6H, 2s, 2 OCH3), 4.26 (2H,
s, CH2), 6.17 (1H, d, 3 JP H = 21.2 Hz, P=C–CH) ppm.
13C NMR (125 MHz, CDCl3): δ = 38.29 (CH2), 39.82
(d, 1 JPC = 90.5 Hz, P=C), 49.03 and 52.29 (2 OCH3),
In this paper, we describe the results of our studies
on a three-component reaction between triphenylphos-
phine, dialkyl acetylenedicarboxylate, and substituted
phthalazin-1(2H)-one that afford novel phosphorane
derivatives (scheme 1). The reaction is created by sim-
ply mixing three common reactants.
On basis of the well-established chemistry of triva-
lent phosphorus as a good nucleophile14,15 it is
known that reaction of phosphorus(III) compounds with
electron deficient alkynes16 consists of an initial
Michael-addition of triphenylphosphine 1 to dialkyl
acetylenedicarboxylates 2, to produce the carbene-ylide
62.06 (d, 2 JPC = 14.6 Hz, P=C–CH), 115.54 (d, 2 JC F
=
7.5 Hz, CH), 124.70 (CH), 127.37 (d, 1 JPC = 91.9 Hz,
3
Cipso), 128.33 (C), 128.56 (d, JPC = 11.9 Hz, Cmeta),
3
129.98 (d, JC F = 7.8 Hz, CH), 132.43 (CH), 133.79
(d, 2 JPC = 8.5 Hz, Cortho), 134.25 (d, 4 JC F = 2.8 Hz, C),
142.95 (C), 162.37 (C=O), 169.90 (d, 2 JPC = 12.5 Hz,
C=O), 171.72 (C=O) ppm. 31P NMR (162.0 MHz,
CDCl3): δ = 22.88 ppm.
2.1h Diethyl 2-[4-fluorobenzyl-1-oxo-2(1H) phtha-
lazinyl]-3-(1,1,1-triphenyl-λ5-phosphanylidene) suc-
cinate (5h): (White powder, 0.60 g, m.p 204–206◦C,
yield 87%) IR (KBr) (νmax, cm−1): 1753, 1651 and 1600
(C=O). Anal. Calcd. For C41H36FN2O5P (686.71): C,
71.71; H, 5.28; N, 4.08%. Found: C, 71.73; H, 5.18; N,
3.99%. Isomer, (E) (50%) 1H NMR (500 MHz, CDCl3):
δ = 1.16 (3H, t, 3 JH H = 7.0 Hz, CH3), 1.29 (3H, t, 3 JH H
X
O
O
COOR
COOR
RO
Ph3P
N
PPh3
+
+
N
NH
N
3
O
= 7.2 Hz, CH3), 4.26 (2H, s, CH2), 6.97 (1H, d, JP H
RO
O
= 20.8 Hz, P=C–CH), 6.94–8.34 (46H, m, arom)*ppm.
13C NMR (125 MHz, CDCl3): δ = 14.10 and 14.15
X
1
(2 CH3), 38.23 (CH2), 40.78 (d, JPC = 139.6 Hz,
2
P=C), 57.65 and 60.93 (2 OCH2), 61.18 (d, JPC
=
Scheme 1. One-pot synthesis of substituted stabilized phos-
2
phorus ylides.
15.8 Hz, P=C–CH), 115.35 (d, JC F = 5.8 Hz, CH),

A facile one-pot three-component reaction leading to phosphorus ylides
1011
+
PPh3
1
ROOC
C
C
COOR
X
2
PPh3
COOR
PPh3
Ph3P
C
O
N
COOR
C
C
C
C
C
C
+
ROOC
NH
OR
ROOC
3
ROOC
4
O
X
O
R
N
N
Ph3P
O
N
N
,
C
C
COOR
H
O
ROOC
O
O
PPh3
5a-h
g
X
O
R
e
a
c
d
h
5
b
f
R
x
CH3 CH3CH2 CH3 CH3CH2 CH3 CH3CH2
OCH3 OCH3
Cl
CH3 CH3CH2
H
H
F
Cl
F
Scheme 2. The plausible mechanism for one-pot synthesis of multifunctionalized stabilized phosphorus ylides.
intermediate 3 which is sufficiently stabilized by res- the mixture of two geometrical isomers of Z and E.
onance.17–20 This is followed by protonation of the Although the presence of the 31P nucleus has com-
1
carbene-ylide intermediate by the NH acid 4. The posi- plicated both the H and 13C NMR spectra of 5a, it
tively charged ion is then attacked by the nitrogen of helps in assignment of signals by long range spin–
1
the conjugated base of NH acid group to afford phtha- spin couplings with H and 13C nuclei. Partial assign-
lazinone derivatives 5 that contain ylide as well as ester ments of these resonances are given in the experi-
moieties (scheme 2).
mental section. The 31P NMR spectrum for compound
Compounds 5a–h are stable solids and their struc- 5a indicated two signals at δ = 22.80 and 23.00 ppm
1
tures are revealed by elemental analyses and IR, H, due to the presence of two geometrical isomers. The
1
13C and 31P NMR spectra. The H, 13C and 31P NMR 1H, 13C and 31P NMR spectra for compound 5b are
spectra of ylides 5a–h are consistent with two isomers. similar to those of 5a, except for ester groups, which
These compounds exist in the solution as two geometri- exhibited characteristic resonances with appropriate
1
cal isomers (Z) and (E); the principal cause of this phe- chemical shifts. The H, 13C and 31P NMR spectral
nomenon is due to the negative charge of ylide moiety data for compound 5c–h are also consistent with the
which is conjugated with the adjacent carbonyl group. proposed structures (see the experimental section). The
1
Rotation around the carbon–carbon double bond is slow structural assignments made on the basis of H and
on the NMR time scale for spontaneous interconver-
sion process between (Z) and (E) geometrical isomers
X
X
at room temperature (scheme 3).
1
The H NMR spectrum of 5a exhibited four sharp
signals (δ = 3.15, 3.55, 3.60 and 3.61 ppm) readily rec-
ognized as arising from methoxy protons along with
two signals for the methylene protons at δ = 4.29
and 4.32 (s, 2H, CH2). The methine proton appeared
Ph3P
O
OR
O
Ph3P
N
N
N
OR
N
at δ = 6.34 and 6.26 ppm, as a doublet (3 JPH
=
CO2R
CO2R
O
O
20.0 Hz) that are consistent with the two isomers.
The aromatic protons appear as a multiplet at δ =
7.20–8.34 ppm for two stereoisomers. 13C and 31P
NMR spectrum of product 5a is in agreement with
5-(Z)
5-(E)
Scheme 3. Geometrical isomers (Z) and (E).

1012
Zahra Hassani and Zeinab Esfandiarpour
13C NMR spectra of compounds 5a–h were supported
by measurements of their IR spectra. The carbonyl
region of the spectrum exhibited three distinct absorp-
tion bands for each compound (see experimental sec-
tion). The special interest is the ester absorption at
1753–1659 cm−1 for these compounds. Conjugation
with the negative charge appears to be a plausible fac-
tor for reduction in wave numbers of the carbonyl
absorption bands.
2. Olmo E, Barboza B, Ybarra M, Lopez-Perez J L,
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In summary, the present study demonestrates that phos-
phorus ylides could be prepared by a simple, effective,
one-pot three-component reaction of acetylenic esters,
NH acids (phthalazin-1(2H)-one) and triphenylphos-
phine. High quality yields of the products and the rel-
atively short reaction times are the main advantages of
this method. The proposed method further carries the
advantage that not only the reactions can be performed
under neutral and mild conditions, but also the starting
materials and reagents can be mixed without any activa-
tion or modification. In view of the widespread biologi-
cal activities of phthalazinones derivatives, the fused
phosphoranes with bioactive phthalazinones deriva-
tives, as prepared in the present study could have use-
ful applications in synthetic organic and bioorganic che-
mistry. The procedure described here may be employed
as an admissible method for the preparation of phos-
phoranes with variable functionalities.
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Acknowledgements
The authors gratefully acknowledge the financial sup-
port by the International Center for Science, High Tech-
nology and Environmental Sciences, Kerman, Iran. We
also thank Dr. A Ahmadi for English language editing
of the manuscript.
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