A simple synthesis of oxaphospholes

Article abstract of DOI:10.1080/10426507.2010.515953

Stable derivatives of oxaphospholes were obtained from the reaction between electron-deficient acetylenic compounds and phenacyl bromide or its derivatives in the presence of triphenylphosphine in acetonitrile as the solvent in excellent yields.

Full text of DOI:10.1080/10426507.2010.515953

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Phosphorus, Sulfur, and Silicon and the
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A Simple Synthesis of Oxaphospholes
Faramarz Rostami Charati a , Zinatossadat Hossaini b & Mohammad
R. Hosseini-Tabatabaei c
a Chemistry Department , Faculty of Science, Gonbad Kavous
University , Gonbad , Iran
b Chemistry Department , Islamic Azad University, Qaemshahr
Branch , Qaemshahr , Iran
c Chemistry Department , Islamic Azad University, Zahedan Branch ,
Zahedan , Iran
Published online: 04 Aug 2011.
To cite this article: Faramarz Rostami Charati , Zinatossadat Hossaini & Mohammad R. Hosseini-
Tabatabaei (2011) A Simple Synthesis of Oxaphospholes, Phosphorus, Sulfur, and Silicon and the
Related Elements, 186:7, 1443-1448, DOI: 10.1080/10426507.2010.515953
To link to this article: http://dx.doi.org/10.1080/10426507.2010.515953
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Phosphorus, Sulfur, and Silicon, 186:1443–1448, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.515953
A SIMPLE SYNTHESIS OF OXAPHOSPHOLES
Faramarz Rostami Charati,1 Zinatossadat Hossaini,2
and Mohammad R. Hosseini-Tabatabaei3
1Chemistry Department, Faculty of Science, Gonbad Kavous University, Gonbad,
Iran
2Chemistry Department, Islamic Azad University, Qaemshahr Branch, Qaemshahr,
Iran
3Chemistry Department, Islamic Azad University, Zahedan Branch,
Zahedan, Iran
GRAPHICAL ABSTRACT
O
RO2C
Ph
CO2R
Br
CO2R
CO2R
Br
CH3CN
r.t., 8 h
PPh3
P
Ph
Ph
O
R'
R'
Abstract Stable derivatives of oxaphospholes were obtained from the reaction between
electron-deficient acetylenic compounds and phenacyl bromide or its derivatives in the presence
of triphenylphosphine in acetonitrile as the solvent in excellent yields.
Keywords Dialkyl acetylenedicarboxylates; multicomponent reaction; oxaphosphole;
triphenylphosphine
INTRODUCTION
In recent years there has been increasing interest in the synthesis of organophosphorus
compounds; that is, those bearing a carbon atom bound directly to a phosphorus atom. This
interest has resulted from the recognition of the value of such compounds in a variety
of biological, industrial, and chemical synthetic uses. A large number of methods have
appeared that describe novel syntheses of organophosphorus compounds.1–3 The successful
attack by nucleophilic trivalent phosphines on a carbon atom is facilitated when the latter
is conjugated with a carbonyl group or when it is part of an unsaturated bond otherwise
activated.1–9 There have been many studies of reactions between trivalent phosphorus
nucleophiles and α,β-unsaturated carbonyl compounds in the presence of a proton source
such as an alcohol or a CH-acid.1,9,10
Received 1 July 2010; accepted 12 August 2010.
Address correspondence to F. Rostami Charati, Chemistry Department, Faculty of Science, Gonbad Kavous
University, P.O. Box 163, Gonbad, Iran. E-mail: frostami@gau.ac.ir
1443

1444
F. ROSTAMI CHARATI ET AL.
We report a simple one-pot, three-component synthesis of 2,5-dihydro-1,2-
oxaphosphole derivatives 4. Thus, the reaction of triphenylphosphine 1 and activated
acetylenic compounds 2 in the presence of phenacyl bromide or its derivatives 3 leads to
1,2-oxaphosphole derivatives 4 (Scheme 1).
O
CO2R
Br
RO2C
Ph
Ph
Ph
CO2R
Br
CH3CN
r.t., 8 h
PPh3
P
O
R'
CO2R
R'
4a-j
(82-92%)
1
2
3
Scheme 1 Synthesis of oxaphosphole derivatives.
RESULTS AND DISCUSSION
As indicated in Scheme 1, the 1:1:1 addition reaction of triphenyphosphine 1 with
dialkyl acetylenedicarboxylates 2 and phenacyl bromide or its derivatives 3 occurs smoothly
at room temperature to produce 1,2-oxaphosphole derivatives 4.
The structures of the products were deduced from their infrared (IR), mass, and 1H-,
13C-, and 31P-NMR spectra. The mass spectra of these compounds displayed molecular
ion peaks at the appropriate m/z values. The 1H-NMR spectrum of 4a in CDCl3 showed a
singlet at 2.36 for the methyl group. The methylene protons of CH2Br were diastereotopic
2
2
and showed two doublets at δ = 4.12 (d, J = 11.0 Hz) and 4.52 (d, J = 11.0 Hz).
Two peaks at 163.0 (d, 2JCP = 24.2 Hz) and 168.4 (d, 3JCP = 21.2 Hz) were observed in
the 13C-NMR spectrum of 4a, which were attributed to the carbonyl groups. The 1H- and
13C-NMR spectra of 4b–4j are similar to those for 4a except for the aromatic moieties and
the substituents in position 4, which show characteristic resonances in appropriate regions
of the spectrum.
To explore the scope of this reaction further, we extended our studies to the reaction
of various dialkyl acetylenedicarboxylates and PPh3 with phenacyl bromide derivatives. As
indicated in Table 1, the reactions proceeded very efficiently in excellent yields. Although
the mechanism of this reaction has not been established, a plausible rationalization can be
advanced to explain product formation (Scheme 2).11
CO2R
RO2C
CO2R
RO2C
Br
+ 3
Ph
Ph
P
4
Ph
Ph
1
+ 2
P
O
Ph
Ph
R'
5
6
Scheme 2 Proposed mechanism for synthesis of oxaphospholes.

A SIMPLE SYNTHESIS OF OXAPHOSPHOLES
1445
Table 1 1,2-Oxaphosphole derivatives
Entry
R
Rꢁ
Compound 4
Yield of 4 (%)
1
2
3
4
5
6
7
8
9
Me
Et
Me
Et
Me
Et
Me
Et
Me
Me
NO2
NO2
Ph
Ph
Cl
Cl
OMe
OMe
4a
4b
4c
4d
4e
4f
4g
4h
4i
85
84
85
87
83
80
84
82
87
83
Me
Et
10
4j
On the basis of the well-established chemistry of trivalent phosphorus nucleophiles,1–5
it is reasonable to assume that 1,2-oxaphosphole 4 results from initial addition of triph-
enylphosphine to the acetylenic compound and subsequent attack of the resulting anion 5
to the carbonyl carbon of phenacyl bromide or its derivatives to yield betaine 6, which ap-
parently cyclizes under the reaction conditions employed to produce the 1,2-oxaphosphole
compounds 4 (Scheme 2).
In conclusion, a convenient one-pot method for the synthesis of 1,2-oxaphosphole
derivatives from readily accessible precursors has been developed. These compounds are
important starting materials in the synthesis of natural products. The present procedure has
advantages such as good yield and neutral reaction conditions.
EXPERIMENTAL
Melting points were taken on a Kofler hot-stage apparatus and are uncorrected.
1H-, 13C-, and 31P-NMR spectra were obtained with a Bruker FT-500 spectrometer in
CDCl3 and tetramethylsilane (TMS) was used as an internal standard. Mass spectra were
recorded with a Finnigan Mat TSQ-70 spectrometer. Infrared (IR) spectra were acquired on
a Nicolet Magna 550-FT spectrometer. Elemental analyses were carried out with a Perkin-
Elmer model 240-C apparatus. The results of elemental analyses (C, H, N) were within
0.4% of the calculated values. Acetylenic ester, phenacyl bromide or its derivatives, and
triphenylphosphine were obtained from Fluka and were used without further purification.
General Procedure for the Preparation of Compounds 4a–j
To a magnetically stirred solution of phenacyl bromide or its derivatives (2 mmol) and
dialkyl acetylenedicarboxylate (2 mmol) in CH3CN (5 mL) was added triphenylphosphine
(2 mmol) slowly at room temperature. The reaction mixture was stirred for 8 h at room
temperature. After completion of the reaction, as indicated by thin-layer chromatography
(TLC; ethyl acetate/n-hexane, 4:1), the solvent was removed under reduced pressure and
the viscous residue was purified by column chromatography (SiO2; hexane/AcOEt 4:1) to
afford the pure title compounds.
Dimethyl
5-(bromomethyl)-5-(4-methylphenyl)-2,2,2-triphenyl-2,5-
dihydro-1,2λ5-oxaphosphole-3,4-dicarboxylate (4a). Yellow crystals, yield: 1.04 g
(85%), m.p. 143–145 ◦C. IR (KBr) (νmax/cm−1): 1726, 1680, 1652, 1263 cm−1; 1H-NMR:

1446
F. ROSTAMI CHARATI ET AL.
δ = 2.36 (3 H, s, Me), 3.78 (3 H, s, MeO), 3.90 (3 H, s, MeO), 4.12 (1 H, d, 2J = 11.0 Hz,
CH), 4.52 (1 H, d, 2J = 11.0 Hz, CH), 7.16 (2 H, d, 3J = 7.6 Hz, 2 CH), 7.33 (2 H, d, 3J =
7.5 Hz, 2 CH), 7.47–7.84 (15 H, m, 15 CH); 13C-NMR: δ = 20.9 (Me), 36.8 (CH2Br), 52.7
(MeO), 52.8 (MeO), 78.7 (d, 2JCP = 23.4 Hz, C), 125.6 (2 CH), 129.2 (d, 3JCP = 21.1 Hz,
6 CH), 129.4 (3 CH), 129.6 (2 CH), 131.9 (d, 2JCP = 31.9 Hz, 6 CH), 132.0 (d, 3JCP = 22.4
Hz, C), 135.1 (d, 1JCP = 230.1 Hz, 3 C), 141.9 (C), 150.4 (d, 1JCP = 192.3 Hz, C), 163.0
(d, 2JCP = 24.2 Hz, C O), 165.1 (d, 2JCP = 22.5 Hz, C), 168.4 (d, 3JCP = 21.2 Hz, C O)
ppm; 31P-NMR (202.5 MHz, CDCl3): 18.92. Anal. Calcd. for C33H30BrPO5 (617.47): C,
64.19; H, 4.90. Found: C, 64.28; H, 5.02. 565 MS, m/z (%): 617 (M+, 15), 586 (85), 555
(72), 355 (54), 262 (96), 31 (100).
Diethyl 5-(bromomethyl)-5-(4-methylphenyl)-2,2,2-triphenyl-2,5-dihydro-
1,2λ5-oxaphosphole-3,4-dicarboxylate (4b). Yellow crystals, yield: 1.08 g (84%),
m.p. 138–140 ◦C. IR (KBr) (νmax/cm−1): 1725, 1678, 1662, 1510, 1260 cm−1; 1H-NMR: δ =
1.15 (3 H, t, 3J = 7.3 Hz, Me), 1.27 (3 H, t, 3J = 7.2 Hz, Me), 2.34 (3 H, s, Me), 4.10 (1
H, d, 2J = 11.2 Hz, CH), 4.25–4.30 (2 H, m, OCH2), 4.32–4.40 (2 H, q, OCH2), 4.45 (1
H, d, 2J = 11.2 Hz, CH), 7.15 (2 H, d, 3J = 7.5 Hz, 2 CH), 7.37 (2 H, d, 3J = 7.8 Hz, 2
CH), 7.42–7.72 (15 H, m, 15CH); 13C-NMR: δ = 13.5 (Me), 14.0 (Me), 21.2 (Me), 37.4
(CH2Br), 60.37 (OCH2), 61.5 (OCH2), 87.5 (d, 2JCP = 20.8 Hz, C), 126.7 (2 CH), 129.3
(d, 3JCP = 23.2 Hz, 6 CH), 129.5 (3 CH), 130.1 (2 CH), 132.2 (d, 2JCP = 32.4 Hz, 6 CH),
132.5 (d, 3JCP = 23.0 Hz, C), 135.6 (d, 1JCP = 235.4 Hz, 3 C), 142.7 (C), 151.0 (d, 1JCP
=
2
2
194.3 Hz, C), 163.5 (d, JCP = 25.4 Hz, C O), 164.8 (d, JCP = 24.0 Hz, C), 167.4
(d, 3JCP = 22.0 Hz, C O) ppm; 31P-NMR (202.5 MHz, CDCl3): 19.21. Anal. Calcd. for
C35H34BrPO5 (645.52): C, 65.12; H, 5.31. Found: C, 65.25; H, 5.42.
Dimethyl 5-(bromomethyl)-5-(4-nitrophenyl)-2,2,2-triphenyl-2,5-dihydro-
1,2λ5-oxaphosphole-3,4-dicarboxylate (4c). Yellow powder, yield: 1.10 g (85%),
m.p. 148–150 ◦C. IR (KBr) (νmax/cm−1): 1738, 1681, 1658, 1585, 1257 cm−1; 1H-NMR:
2
δ = 3.79 (3 H, s, MeO), 3.90 (3 H, s, MeO), 4.16 (1 H, d, J = 11.2 Hz, CH), 4.44 (1
H, d, 2J = 11.2 Hz, CH), 7.68 (2 H, d, 3J = 8.5 Hz, 2 CH), 7.72–8.14 (15 H, m, 15 CH),
8.23 (2 H, d, 3J = 8.5 Hz, 2 CH); 13C-NMR: δ = 35.8 (CH2Br), 53.1 (MeO), 53.4 (MeO),
2
3
89.9 (d, JCP = 22.7 Hz, C), 123.8 (2 CH), 127.4 (2 CH), 129.5 (d, JCP = 24.0 Hz, 6
2
1
CH), 130.0 (3 CH), 132.2 (d, JCP = 32.4 Hz, 6 CH), 135.6 (d, JCP = 235.4 Hz, 3 C),
143.7 (C), 148.0 (d, 3JCP = 25.0 Hz, C), 150.5 (d, 1JCP = 197.6 Hz, C), 164.2 (d, 2JCP
=
26.0 Hz, C O), 165.2 (d, 2JCP = 26.4 Hz, C), 168.7 (d, 3JCP = 25.2 Hz, C O) ppm; 31P-
NMR (202.5 MHz, CDCl3): 18.94. Anal. Calcd. for C32H27BrNPO7 (648.44): C, 59.27; H,
4.20; N, 2.16. Found: C, 59.35; H, 4.28; N, 2.24.
Diethyl 5-(bromomethyl)-5-(4-nitrophenyl)-2,2,2-triphenyl-2,5-dihydro-
1,2λ5-oxaphosphole-3,4-dicarboxylate (4d). Orange powder, yield: 0.86 g (87%),
m.p. 163–165 ◦C. IR (KBr) (νmax/cm−1): 1738, 1684, 1653, 1545, 1249 cm−1; 1H-NMR:
3
3
2
δ = 1.23 (3 H, t, J = 7.2 Hz, Me), 1.34 (3 H, t, J = 7.4 Hz, Me), 4.15 (1 H, d, J =
11.5 Hz, CH), 4.23–4.30 (2 H, m, OCH2), 4.34 (1 H, d, 2J = 11.5 Hz, CH), 4.38 (2 H, q,
3J = 7.5 Hz, OCH2), 7.67 (2 H, d, 3J = 8.4 Hz, 2 CH), 7.70–8.16 (15 H, m, 15 CH), 8.22
(2 H, d, J = 8.4 Hz, 2 CH); 13C-NMR: δ = 14.0 (Me), 14.5 (Me), 36.8 (CH2Br), 61.4
3
(OCH2), 62.0 (OCH2), 90.0 (d, 2JCP = 23.0 Hz, C), 124.8 (2 CH), 128.2 (2 CH), 129.6 (d,
3JCP = 23.8 Hz, 6 CH), 130.5 (3 CH), 132.8 (d, 2JCP = 33.4 Hz, 6 CH), 135.2 (d, 1JCP
=
3
1
237.3 Hz, 3 C), 143.5 (C), 148.4 (d, JCP = 26.7 Hz, C), 151.2 (d, JCP = 200.2 Hz,
2
2
3
C), 163.8 (d, JCP = 25.7 Hz, C O), 165.5 (d, JCP = 26.4 Hz, C), 168.6 (d, JCP
=
25.5 Hz, C O) ppm; 31P-NMR (202.5 MHz, CDCl3): 19.00. Anal. Calcd. for
C34H31BrNPO7 (676.49): C, 60.37; H, 4.62; N, 2.07. Found: C, 60.29; H, 4.56; N, 2.00.

A SIMPLE SYNTHESIS OF OXAPHOSPHOLES
1447
Dimethyl 5-(bromomethyl)-5-(4-biphenyl)-2,2,2-triphenyl-2,5-dihydro-
1,2λ5-oxaphosphole-3,4-dicarboxylate (4e). Yellow powder, yield: 1.13 g (83%),
◦
1
m.p. 146–148 C. IR (KBr) (νmax/cm−1): 175, 1674, 1658, 1583, 1270 cm−1; H-NMR:
2
δ = 3.82 (3 H, s, MeO), 3.90 (3H, s, MeO), 4.23 (1 H, d, J = 11.2 Hz, CH), 4.54 (1 H,
2
3
3
d, J = 11.2 Hz, CH), 7.34 (1 H, t, J = 7.6 Hz, CH), 7.42 (2 H, t, J = 7.6 Hz, 2 CH),
3
3
3
7.65 (2 H, d, J = 7.6 Hz, 2 CH), 7.67 (2 H, d, J = 8.2 Hz, 2 CH), 7.74 (2 H, d, J =
8.2 Hz, 2 CH), 7.78–7.94 (15 H, m, 15 CH); 13C-NMR: δ = 38.5 (CH2Br), 52.8 (MeO),
53.0 (MeO), 89.0 (d, 2JCP = 24.2 Hz, C), 127.2 (2 CH), 127.8 (2 CH), 128.0 (2 CH), 128.2
(CH), 129.0 (2 CH), 129.5 (d, 3JCP = 24.6 Hz, 6 CH), 131.3 (3 CH), 133.0 (d, 2JCP = 33.2
Hz, 6 CH), 135.6 (d, 1JCP = 236.4 Hz, 3 C), 138.0 (C), 142.6 (C), 143.2 (d, 3JCP = 27.3
Hz, C), 151.4 (d, 1JCP = 200.3 Hz, C), 164.5 (d, 2JCP = 26.8 Hz, C O), 166.8 (d, 2JCP
=
27.6 Hz, C), 168.5 (d, 3JCP = 25.8 Hz, C O) ppm; 31P-NMR (202.5 MHz, CDCl3): 18.25.
Anal. Calcd. for C38H32BrPO5 (679.54): C, 67.16; H, 4.75. Found: C, 67.25; H, 4.82.
Diethyl
5-(bromomethyl)-5-(4-biphenyl)-2,2,2-triphenyl-2,5-dihydro-
1,2λ5-oxaphosphole-3,4-dicarboxylate (4f). Yellow powder, yield: 1.13 g (80%),
m.p. 152–154 ◦C. IR (KBr) (νmax/cm−1): 1724, 1675, 1658, 1582, 1270 cm−1; 1H-NMR:
3
3
2
δ = 1.28 (3 H, t, J = 7.5 Hz, Me), 1.35 (3 H, t, J = 7.4 Hz, Me), 4.14 (1 H, d, J =
3
11.0 Hz, CH), 4.38–4.42 (2 H, m, OCH2), 4.45 (2 H, q, J = 7.3 Hz, OCH2), 4.57 (1 H,
2
3
3
d, J = 11.0 Hz, CH), 7.37 (1 H, t, J = 7.6 Hz, CH), 7.45 (2 H, t, J = 7.5 Hz, 2 CH),
3
3
3
7.50 (2 H, d, J = 7.6 Hz, 2 CH), 7.57 (2 H, d, J = 8.4 Hz, 2 CH), 7.61 (2 H, d, J =
8.4 Hz, 2 CH), 7.65–7.84 (15 H, m, 15 CH); 13C-NMR: δ = 14.0 (Me), 14.2 (Me), 36.7
(CH2Br), 60.2 (OCH2), 61.8 (OCH2), 89.5 (d, 2JCP = 25.0 Hz, C), 127.0 (2 CH), 127.5 (2
CH), 127.8 (2 CH), 128.0 (CH), 128.9 (2 CH), 129.6 (d, 3JCP = 24.5 Hz, 6 CH), 131.5 (3
CH), 132.8 (d, 2JCP = 32.5 Hz, 6 CH), 134.3 (d, 1JCP = 235.8 Hz, 3 C), 140.4 (C), 142.7
3
1
2
(C), 143.0 (d, JCP = 28.4 Hz, C), 151.6 (d, JCP = 198.6 Hz, C), 165.3 (d, JCP = 27.0
Hz, C O), 167.2 (d, 2JCP = 27.5 Hz, C), 168.5 (d, 3JCP = 25.8 Hz, C O) ppm; 31P-NMR
(202.5 MHz, CDCl3): 18.58. Anal. Calcd. for C40H36BrPO5 (707.59): C, 67.90; H, 5.13.
Found: C, 67.95; H, 5.22.
Dimethyl
5-(bromomethyl)-5-(4-chlorophenyl)-2,2,2-triphenyl-2,5-
dihydro-1,2λ5-oxaphosphole-3,4-dicarboxylate (4g). Pale yellow powder, yield:
1.07 g (84%), m.p. 142–144 C. IR (KBr) (νmax/cm−1): 1732, 1675, 1642, 1545, 1252
◦
cm−1; 1H-NMR: δ = 3.75 (3 H, s, MeO), 3.92 (3 H, s, MeO), 4.12 (1 H, d, 2J = 11.0 Hz,
CH), 4.45 (1 H, d, 2J = 11.0 Hz, CH), 7.35 (2 H, d, 3J = 8.0 Hz, 2 CH), 7.42 (2 H, d, 3J =
7.9 Hz, 2 CH), 7.52–7.76 (15 H, m, 15 CH); 13C-NMR: δ = 38.4 (CH2Br), 52.4 (MeO),
2
3
53.4 (MeO), 90.4 (d, JCP = 26.0 Hz, C), 127.8 (2 CH), 128.4 (2 CH), 128.9 (d, JCP
=
2
1
24.2 Hz, 6 CH), 131.0 (3 CH), 132.6 (d, JCP = 32.6 Hz, 6 CH), 133.9 (d, JCP = 236.2
3
1
Hz, 3 C), 137.2 (d, JCP = 27.6 Hz, C), 143.0 (C), 152.0 (d, JCP = 197.8 Hz, C), 166.1
(d, 2JCP = 28.2 Hz, C O), 169.4 (d, 2JCP = 28.4 Hz, C), 170.2 (d, 3JCP = 26.2 Hz, C O)
ppm; 31P-NMR (202.5 MHz, CDCl3): 18.62. Anal. Calcd. for C32H27BrClPO5 (637.88):
C, 60.25; H, 4.27. Found: C, 60.34; H, 4.35.
Diethyl 5-(bromomethyl)-5-(4-chlorophenyl)-2,2,2-triphenyl-2,5-dihydro-
1,2λ5-oxaphosphole-3,4-dicarboxylate (4h). Yellow powder, yield: 1.09 g (82%),
m.p. 168–170 ◦C. IR (KBr) (νmax/cm−1): 1725, 1680, 1652, 1584, 1275 cm−1; 1H-NMR:
δ = 1.25 (3 H, t, 3J = 7.3 Hz, Me), 1.32 (3 H, t, 3J = 7.3 Hz, Me), 4.18 (1 H, d, 2J = 11.3 Hz,
CH), 4.22–4.28(2 H, m, OCH2), 4.38 (2 H, q, 3J = 7.5Hz, OCH2), 4.42(1H, d, 2J = 11.3 Hz,
3
3
CH), 7.35 (2 H, d, J = 8.0 Hz, 2 CH), 7.43 (2 H, d, J = 8.0 Hz, 2 CH), 7.54–7.78 (15
H, m, 15 CH); 13C-NMR: δ = 13.5 (Me), 14.2 (Me), 37.7 (CH2Br), 62.7 (OCH2), 62.5
2
3
(OCH2), 90.2 (d, JCP = 26.4 Hz, C), 127.6 (2 CH), 128.3 (2 CH), 129.2 (d, JCP
=

1448
F. ROSTAMI CHARATI ET AL.
2
1
24.5 Hz, 6 CH), 131.5 (3 CH), 132.7 (d, JCP = 32.5 Hz, 6 CH), 134.0 (d, JCP
=
3
1
235.8 Hz, 3 C), 137.5 (d, JCP = 28.2 Hz, C), 143.2 (C), 152.3 (d, JCP = 199.2 Hz, C),
2
2
3
166.5 (d, JCP = 28.5 Hz, C O), 169.5 (d, JCP = 28.6 Hz, C), 170.6 (d, JCP = 26.3
Hz, C O) ppm; 31P-NMR (202.5 MHz, CDCl3): 18.86. Anal. Calcd. for C34H31BrClPO5
(665.94): C, 61.32; H, 4.69. Found: C, 61.45; H, 4.76.
Dimethyl
5-(bromomethyl)-5-(4-methoxyphenyl)-2,2,2-triphenyl-2,5-
dihydro-1,2λ5-oxaphosphole-3,4-dicarboxylate (4i). Yellow crystals, yield: 1.10
g (87%), m.p. 145–147 C. IR (KBr) (νmax/cm−1): 1726, 162, 1657, 1585, 1263 cm−1
;
◦
1H-NMR: δ = 3.75 (3 H, s, MeO), 3.80 (3 H, s, MeO), 3.95 (3 H, s, MeO), 4.15 (1 H, d,
2J = 11.5 Hz, CH), 4.55 (1 H, d, 2J = 11.5 Hz, CH), 7.00 (2 H, d, 3J = 8.5 Hz, 2 CH), 7.35
(2 H, d, 3J = 8.5 Hz, 2 CH), 7.56–7.82 (15 H, m, 15 CH); 13C-NMR: δ = 37.0 (CH2Br),
2
52.5 (MeO), 52.8 (MeO), 53.4 (MeO), 89.4 (d, JCP = 27.0 Hz, C), 113.2 (2 CH), 128.5
3
2
(2 CH), 129.5 (d, JCP = 25.4 Hz, 6 CH), 132.1 (3 CH), 132.8 (d, JCP = 32.6 Hz, 6
1
3
CH), 135.4 (d, JCP = 236.0 Hz, 3 C), 137.8 (d, JCP = 28.5 Hz, C), 148.7 (C), 152.5
(d, 1JCP = 198.4 Hz, C), 165.8 (d, 2JCP = 25.7 Hz, C O), 168.3 (d, 2JCP = 28.5 Hz, C),
169.2 (d, 3JCP = 26.3 Hz, C O); 31P-NMR (202.5 MHz, CDCl3): 19.02. Anal. Calcd. for
C33H30BrPO6 (633.47): C, 62.57; H, 4.77. Found: C, 62.68; H, 4.82.
Diethyl
5-(bromomethyl)-5-(4-methoxyphenyl)-2,2,2-triphenyl-2,5-
dihydro-1,2λ5-oxaphosphole-3,4-dicarboxylate (4j). Pale yellow crystals, yield:
1.09 g (83%), m.p. 153–155 C. IR (KBr) (νmax/cm−1): 1735, 1672, 1643, 1564, 1235
◦
cm−1; 1H-NMR: δ = 1.24 (3 H, t, 3J = 7.2 Hz, Me), 1.35 (3 H, t, 3J = 7.3 Hz, Me), 4.15
(1 H, d, 2J = 11.0 Hz, CH), 4.25–4.32 (2 H, m, OCH2), 4.35 (2 H, q, 3J = 7.3 Hz, OCH2),
4.54 (1 H, d, 2J = 11.0 Hz, CH), 6.85 (2 H, d, 3J = 8.4 Hz, 2 CH), 7.30 (2 H, d, 3J = 8.5 Hz,
2 CH), 7.45–7.67 (15 H, m, 15 CH); 13C-NMR: δ = 13.2 (Me), 14.5 (Me), 37.3 (CH2Br),
53.4 (MeO), 62.5 (OCH2), 62.8 (OCH2), 90.7 (d, 2JCP = 26.7 Hz, C), 114.5 (2 CH), 127.4
(2 CH), 130.0 (d, 3JCP = 26.2 Hz, 6 CH), 131.8 (3 CH), 132.6 (d, 2JCP = 31.4 Hz, 6 CH),
135.6 (d, 3JCP = 28.6 Hz, C), 136.2 (d, 1JCP = 237.2 Hz, 3 C), 148.4 (C), 152.4 (d, 1JCP
=
2
2
198.5 Hz, C), 165.5 (d, JCP = 25.6 Hz, C O), 168.7 (d, JCP = 28.7 Hz, C), 169.4 (d,
3JCP = 26.3 Hz, C O) ppm; 31P-NMR (202.5 MHz, CDCl3): 19.21. Anal. Calcd. for
C35H34BrPO6 (661.52): C, 63.55; H, 5.18. Found: C, 63.64; H, 5.26.
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