Three-component reaction of triphenylphosphine, dialkyl acetylenedicarboxylates, and heterocyclic rings and the related iminophosphoranes

Article abstract of DOI:10.1080/00397911.2010.523158

Crystalline phosphorus ylides are obtained in excellent yields from the 1:1:1 addition reaction of triphenylphosphine, dialkyl acetylenedicarboxylate, and NH acids, such as 2-aminothiazole and 2-aminobenzothiazole. These stabilized phosphoranes undergo a

Full text of DOI:10.1080/00397911.2010.523158

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Three-Component Reaction of
Triphenylphosphine, Dialkyl
Acetylenedicarboxylates, and
Heterocyclic Rings and the Related
Iminophosphoranes
Mohammad Anary-Abbasinejad a , Alireza Hassanabadi b & Zahra
Khaksari a
a Department of Chemistry, Islamic Azad University, Yazd Branch,
Yazd, Iran
b Department of Chemistry, Islamic Azad University, Zahedan
Branch, Zahedan, Iran
Accepted author version posted online: 26 Jul 2011.Published
online: 14 Sep 2011.
To cite this article: Mohammad Anary-Abbasinejad , Alireza Hassanabadi & Zahra Khaksari
(2012) Three-Component Reaction of Triphenylphosphine, Dialkyl Acetylenedicarboxylates,
and Heterocyclic Rings and the Related Iminophosphoranes, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 42:2, 204-212, DOI:
10.1080/00397911.2010.523158
To link to this article: http://dx.doi.org/10.1080/00397911.2010.523158
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Synthetic Communications1, 42: 204–212, 2012
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2010.523158
THREE-COMPONENT REACTION OF
TRIPHENYLPHOSPHINE, DIALKYL
ACETYLENEDICARBOXYLATES, AND HETEROCYCLIC
RINGS AND THE RELATED IMINOPHOSPHORANES
Mohammad Anary-Abbasinejad,1 Alireza Hassanabadi,2 and
Zahra Khaksari1
1Department of Chemistry, Islamic Azad University, Yazd Branch, Yazd,
Iran
2Department of Chemistry, Islamic Azad University, Zahedan Branch,
Zahedan, Iran
GRAPHICAL ABSTRACT
Abstract Crystalline phosphorus ylides are obtained in excellent yields from the 1:1:1
addition reaction of triphenylphosphine, dialkyl acetylenedicarboxylate, and NH acids,
such as 2-aminothiazole and 2-aminobenzothiazole. These stabilized phosphoranes undergo
a smooth intramolecular reaction in boiling toluene to produce aryliminophosphoranes in
excellent yields.
Keywords Dialkyl acetylenedicarboxylates; iminophosphoranes; phosphorus ylides;
thiazoles; triphenylphosphine
INTRODUCTION
Iminophosphoranes are important reagents and intermediates, recently, they
have been used for the introduction of imine unit organic synthesis.[1,2] In the
realm of ylide compounds and their value for a variety of industrial, biological,
and chemical synthetic uses, phosphorus ylides are playing increasingly pivotal roles[3]
They has provided chemists with exceptionally fertile ground for the design and
development of new bond formation.[4] Since the pioneering work by Staudinger
Received July 29, 2010.
Address correspondence to Alireza Hassanabadi, Department of Chemistry, Islamic Azad
University, Zahedan Branch, P. O. Box 98135-978, Zahedan, Iran. E-mail: ar_hasanabadi@yahoo.com
204

IMINOPHOSPHORANES
205
and Meyre in 1919,[5] on the preparation of iminophosphoranes, compounds of
general structure R3PNR, the synthetic application of phosphorus ylides to the prep-
aration of various organic products has increased enormously, especially during the
past three decades.[6] Several methods for the preparation of iminophophoranes have
been developed.[7–9]
Phosphonium salts are also prepared by Michael addition of phosphorus
nucleophiles to activated olefins.[10,11] Reaction of acetylenic esters with triphenyl-
phosphine in the presence of an organic compound possessing an acidic hydrogen
recently has been reported to produce phosphorus ylides.[12–14] In continuation of
our work on the reaction between triphenylphosphine and acetylene diesters in the
presence of organic N-H, O-H, or C-H acids,[15–21] we herein report an efficient
synthetic route to stable phosphorus ylides using a three-component reaction of
triphenylphosphine, dialkyl acetylenedicarboxylate (DAAD) and NH acids, such
as 2-aminothiazole and 2-aminobenzothiazole. These stabilized phosphoranes
undergo a smooth intramolecular reaction in boiling toluene to produce arylimino-
phosphoranes 5 in excellent yields.
The reaction of the thiazoles 1 with DAAD 2 in the presence of triphenylpho-
sphine 3 leads to the corresponding ylide 4 in good yields (Scheme 1).
The ylides 4a, b were converted to iminophosphoranes 5a, b when the reaction
mixture was refluxed in toluene (Scheme 2).
Because the rotation about the partial double bond in E and Z isomers is slow
on the NMR time scale at ambient temperature (Scheme 3), the presence of a
mixture of two geometrical isomers E and Z for compounds 4a–d was proven by
1
1
their 13C NMR and H NMR absorption. For example, H NMR and 13C NMR
spectra of these compounds show four singlets for methyl hydrogens and four
absorptions for carbonyl groups, respectively, which are indicative of the presence
Scheme 1. Three-component reaction of triphenylphosphine, DAADs, and thiazoles.

206
M. ANARY-ABBASINEJAD, A. HASSANABADI, AND Z. KHAKSARI
Scheme 2. Reaction mixture refluxed in toluene.
of two isomers. Presence of the 31P nucleus helps in assignment of compounds 4a–d
1
by long-range spin–spin coupling constants of 31P with H and 13C nuclei.
The mass spectrum of compound 4a showed the molecular ion peak at 504.
The 1H NMR spectrum of compound 4a shows four different sharp lines at
d ¼ 3.11, 3.07, 3.57, and 3.68 ppm, which are due to the methoxy protons and two
3
doublet at 4.36 and 4.45 (3JPH ¼ 5 Hz, JHH ¼ 10 Hz, P C-CH) for methine proton,
=
which is coupled with phosphorus atom and NH, two fairly broad signals at d ¼ 6.72
and 6.91 ppm related to protons of N-H groups, and multiplets between 6.32 and
7.68 ppm for aromatic protons. The 13C NMR of compound 4a is in good agreement
with the proposed structure of this compound. The 31P NMR spectrum of
compound 4a consists of two signals at 23.09 and 23.15 ppm. This shift is similar
to those observed for other stable phosphorus ylides.[22,23] The infrared (IR)
spectrum showed an absorption bond at 3365 cmꢀ1 for the NH group. The carbonyl
stretching vibration was observed as strong absorption bonds at 1741 cmꢀ1
.
1
The H NMR spectrum of compound 5a shows two doublet at 6.39 and 6.95
(3JHH ¼ 3.8 Hz,) for thiazole protons and multiplets between 7.43 and 7.83 ppm
for aromatic protons. The 13C NMR spectrum of compound 5a showed seven dis-
tinct resonances in agreement with the proposed structure. Signals of triphenylpho-
1
sphine group appear at 129.05 (2JPC ¼ 12 Hz), 129.28 (d, JPC ¼ 100 Hz), 132.60
Scheme 3. Two rotamers.

IMINOPHOSPHORANES
207
Scheme 4. Suggested mechanism for formation of ylides 4 and iminophosphoranes 5.
(d, 4JPC ¼ 3 Hz), and 133.52 (d, 3JPC ¼ 10 Hz). The 31P NMR spectrum of compound
5a consists of one signal at 15.58 ppm.
It is reasonable to assume that ylide 4 results from the initial addition of
triphenylphosphine to DAAD and subsequent protonation of the 1:1 adduct by
the NH-acidic thiazole. The positively charged ion 7 is then attacked by the anion
6 to form the phosphorane 4. In the ylide 4 in boiling toluene, the NH-proton shifts
to the ylidic carbon and forms the phosphorus betaine 8. This betaine can be in
equilibrium with the azaphosphetane 9. Formation of dimethyl fumarate and=or
dimethyl maleate 4 confirms the proposed mechanism (Scheme 4).
In summary, we report herein that the three-component reaction of triphenyl-
phosphine, DAAD, and NH acids, such as 2-aminothiazole and 2-aminobenzothia-
zole, produces functionalized phosphoranes in good yields. These stabilized
phosphoranes undergo a smooth intramolecular reaction in boiling toluene to produce
aryliminophosphoranes in excellent yields. The advantages of the reported method are
simple available starting materials, short reaction time, simple workup, neutral reac-
tion conditions, and good yields.
EXPERIMENTAL
Melting points were determined with an Electrothermal 9100 apparatus.
Elemental analyses were performed using a Costech ECS 4010 CHNS-O analyzer
at the analytical laboratory of Islamic Azad University, Yazd branch. Mass spectra
were recorded on a Finnigan-mat 8430 mass spectrometer operating at an ionization
potential of 70 eV. IR spectra were recorded on a Shimadzu IR-470 spectrometer.
1H, 13C, and 31P NMR spectra were recorded on Bruker DRX-500 Avance spec-
trometer at solution in CDCl3 using tetramethylsilane (TMS) as internal standard.
The chemicals used in this work were purchased from Fluka (Buchs, Switzerland)
and were used without further purification.

208
M. ANARY-ABBASINEJAD, A. HASSANABADI, AND Z. KHAKSARI
General Procedure for Preparation of Compounds 4a–d
A mixture of dialkyl acetylenedicarboxylate (2 mmol) in dichloromethane
(3 mL) was added dropwise to a magnetically stirred solution of triphenylphosphine
(2 mmol) and thiazole (2 mmol) in dichloromethane (10 mL) at room temperature over
2 min. The reaction mixture was then stirred for 2 h. The resulted precipitate was
filtered off and then recrystallized from 1:1 hexane–ethyl acetate.
General Procedure for Preparation of Compounds 5a, b
A mixture of 4 (1 mmol) in toluene (10 mL) was refluxed for 12 h. The solvent
was removed under reduced pressure, and the residue was purified by silica-gel
column chromatography using hexane–ethyl acetate as eluent. The solvent was
removed under reduced pressure to afford the product.
Dimethyl 2-(Thiazole-2-ylamino)-3-(triphenyl-k5-phosphanylidene)-
succinate (4a)
Yield: 90%; white powder; mp 152–154 ꢁC. IR (KBr) (nmax, cmꢀ1): 3365 (NH),
=
1741 (C O, ester). Calcd. for (C27H25N2O4PS): C, 64.27; H, 4.99; N, 5.55;%. Found:
C, 64.43; H, 4.86; N, 5.59%. MS (m=z, %): 504 (M, 11).
Major isomer (70%). 1H NMR (CDCl3): d ¼ 3.11 (3H, s, OCH3), 3.68 (3H,
3
3
s, OCH3), 4.45 (1H, dd, JHP ¼ 5 Hz, JHH ¼ 10 Hz, P-C-CH), 6.91 (1H, d,
3JHH ¼ 10 Hz, NH), 6.32 (1H, d, 3JHH ¼ 3.8 Hz, CH of C3H2NS), 6.74 (1H, d, 3JHH
¼
3.8 Hz, CH of C3H2NS) 7.26 –7.68 (15H, m, 3C6H5).ꢂ (ꢂFor two conformational iso-
2
mers.) 13C NMR (CDCl3): d ¼ 50.06 (d, 1JPC ¼ 123 Hz, C P), 58.20 (d, JPC ¼ 13 Hz,
=
CH), 49.46, 52.66 (2 OCH3), 106.78, 139.09, 174.15 (3C C3H2NS), 126.99 (d, 1JPC
¼
4
3
92 Hz), 129.03 (2JPC ¼ 12 Hz), 132.29 (d, JPC ¼ 3 Hz), 134.23 (d, JPC ¼ 10 Hz).
169.34 (d, 2JPC ¼ 12 Hz, C O), 170.49 (d, JPC ¼ 12 Hz, C O). 31P NMR (CDCl3):
3
ꢂ
ꢂ
=
=
d 23. 15.
Minor isomer (30%). 1H NMR (CDCl3): d ¼ 3.07 (3H, s, OCH3), 3.57 (3H,
3
3
3
s, OCH3), 4.36 (1H, dd, JHP ¼ 5 Hz, JHH ¼ 10 Hz, P-C-CH), 6.72 (1H, d, JHH
¼
10 Hz, NH), 6.25 (1H, d, 3JHH ¼ 3.8 Hz, CH of C3H2NS), 6.43 (1H, d, 3JHH ¼ 3.8 Hz,
CH of C3H2NS). 13C NMR (CDCl3): d ¼ 50.16 (d, JPC ¼ 123 Hz, C P), 58.34 (d,
1
=
2JPC ¼ 13 Hz, CH), 49.38, 52.71 (2 OCH3), 107.14, 139.01, 174.17 (3C C3H2NS),
126.75 (d, JPC ¼ 92 Hz), 129.18 (2JPC ¼ 12 Hz), 132.43 (d, JPC ¼ 3 Hz), 134.05 (d,
1
4
3JPC ¼ 10 Hz). 31P NMR (CDCl3): d 23.09.
Dimethyl 2-(Benzothiazole-2-ylamino)-3-(triphenyl-k5-
phosphanylidene)-succinate (4b)
Yield: 93%; white powder; mp 157–159 ꢁC. IR (KBr) (nmax, cmꢀ1): 3390 (NH),
=
1744 (C O, ester). Calcd. for (C31H27N2O4PS): C, 67.14; H, 4.91; N, 5.05%. Found:
C, 67.28; H, 4.97; N, 4.96%. MS (m=z, %): 554 (M, 7).
Major isomer (60%). 1H NMR (CDCl3): d ¼ 3.28 (3H, s, OCH3), 3.56 (3H, s,
3
3
3
OCH3), 4.52 (1H, dd, JHP ¼ 5 Hz, JHH ¼ 10 Hz, P-C-CH), 6.88 (1H, d, JHH
¼
10 Hz, NH), 6.99–8.23 (19H, m, aromatic).ꢂ (ꢂFor two conformational isomers.)

IMINOPHOSPHORANES
209
1
2
13C NMR (CDCl3): d ¼ 50.12 (d, JPC ¼ 123 Hz, C P), 58.37 (d, JPC ¼ 13 Hz, CH),
=
49.57, 52.73 (2 OCH3), 118.41, 121.26, 121.44, 125.92, 133.03, 153.08, 174.12 (7C
¼
benzothiazole), 129.66 (2JPC ¼ 12 Hz), 127.68 (d, JPC ¼ 92 Hz), 131.39 (d, JPC
1
4
3
2
ꢂ
=
3 Hz), 133.03 (d, JPC ¼ 10 Hz), 168.96 (d, JPC ¼ 12 Hz, C O), 171.08 (d,
JPC ¼ 12 Hz, C O). 31P NMR (CDCl3): d 22.45.
3
ꢂ
=
Minor isomer (40%). 1H NMR (CDCl3): d ¼ 2.94 (3H, s, OCH3), 3.53 (3H,
3
3
3
s, OCH3), 4.46 (1H, dd, JHP ¼ 5 Hz, JHH ¼ 10 Hz, P-C-CH), 6.86 (1H, d, JHH
¼
10 Hz, NH), 13C NMR (CDCl3): d ¼ 50.10 (d, JPC ¼ 123 Hz, C P), 58.42 (d,
1
=
2JPC ¼ 13 Hz, CH), 49.60, 52.69 (2 OCH3), 118.45, 121.20, 121.32, 125.87, 133.08,
153.12, 174.00 (7C benzothiazole), 129.45 (2JPC ¼ 12 Hz), 127.61 (d, JPC ¼ 92 Hz),
1
131.32 (d, JPC ¼ 3 Hz), 133.09 (d, JPC ¼ 10 Hz). 31P NMR (CDCl3): d 23.49.
4
3
Diethyl 2-(Thiazole-2-ylamino)-3-(triphenyl-k5-phosphanylidene)-
succinate (4c)
Yield: 95%; white powder; mp 168–170 ꢁC. IR (KBr) (nmax, cmꢀ1): 3386 (NH),
=
1748 (C O, ester). Calcd. for (C29H29N2O4PS): C, 65.40; H, 5.49; N, 5.26%. Found:
C, 65.51; H, 5.40; N, 5.18%. MS (m=z, %): 532 (M, 4).
Major isomer (75%). 1H NMR (CDCl3): d ¼ 1.23 and 1.35 (6H, 2 t
3
3JHH ¼ 7 Hz, 2 CH3), 3.36 and 4.25 (4H, 2q JHH ¼ 7 Hz, 2 OCH2), 4.62 (1H, dd,
3
3
3JHP ¼ 5 Hz, JHH ¼ 10 Hz, P-C-CH), 6.92 (1H, d, JHH ¼ 10 Hz, NH), 6.30 (1H, d,
3JHH ¼ 3.8 Hz, CH of C3H2NS), 6.77 (1H, d, JHH ¼ 3.8 Hz, CH of C3H2NS)
3
7.13–7.72 (15H, m, 3C6H5).ꢂ (ꢂFor two conformational isomers.) 13C NMR (CDCl3):
1
2
=
d ¼ 13.50 and 13.81 (2 CH3), 49.95 (d, JPC ¼ 123 Hz, C P), 57,76 (d, JPC ¼ 13 Hz,
CH), 62.07 and 62.31 (2 OCH2), 107.19, 138.87, 174.35 (3C C3H2NS), 127.16
¼
(d, JPC ¼ 92 Hz), 129.27 (2JPC ¼ 12 Hz), 132.47 (d, JPC ¼ 3 Hz), 134.07 (d, JPC
1
4
3
10 Hz). 168.89 (d, JPC ¼ 12 Hz, C O) , 171.32 (d, JPC ¼ 12 Hz, C O). 31P NMR
2
3
ꢂ
ꢂ
=
=
(CDCl3): d 22.75.
Minor isomer (25%). 1H NMR (CDCl3): d ¼ 1.17 and 1.33 (6H, 2 t
3
3JHH ¼ 7 Hz, 2 CH3), 3.52 and 4.20 (4H, 2q JHH ¼ 7 Hz, 2 OCH2), 4.69 (1H, dd,
3
3
3JHP ¼ 5 Hz, JHH ¼ 10 Hz, P-C-CH), 6.70 (1H, d, JHH ¼ 10 Hz, NH), 6.18 (1H, d,
3JHH ¼ 3.8 Hz, CH of C3H2NS), 6.79 (1H, d, JHH ¼ 3.8 Hz, CH of C3H2NS). 13C
3
1
=
NMR (CDCl3): d ¼ 13.52 and 13.78 (2 CH3), 49.90 (d, JPC ¼ 123 Hz, C P), 57.86
2
(d, JPC ¼ 13 Hz, CH), 62.01 and 62.16 (2 OCH2), 107.08, 138.94, 174.30 (3C
C3H2NS), 127.47 (d, JPC ¼ 92 Hz), 129.36 (2JPC ¼ 12 Hz), 132.56 (d, JPC ¼ 3 Hz),
1
4
134.23 (d, JPC ¼ 10 Hz). 31P NMR (CDCl3): d 22.83.
3
Diethyl 2-(Benzothiazole-2-ylamino)-3-(triphenyl-k5-phosphanylidene)-
succinate (4d)
Yield: 90%; white powder; mp 163–165 ꢁC. IR (KBr) (nmax, cmꢀ1): 3360 (NH),
=
1735 (C O, ester). Calcd. for (C33H31N2O4PS): C, 68.03; H, 5.36; N, 4.81%. Found:
C, 68.15; H,5.21; N, 4.77%. MS (m=z, %): 582 (M, 9).
Major isomer (70%). 1H NMR (CDCl3): d ¼ 1.20 and 1.42 (6H, 2 t
3
3JHH ¼ 7 Hz, 2 CH3), 3.47 and 4.18 (4H, 2q JHH ¼ 7 Hz, 2 OCH2), 4.69 (1H, dd,

210
M. ANARY-ABBASINEJAD, A. HASSANABADI, AND Z. KHAKSARI
3
3
3JHP ¼ 5 Hz, JHH ¼ 10 Hz, P-C-CH), 6.99 (1H, d, JHH ¼ 10 Hz, NH), 7.13–7.71
(19H, m, aromatic).ꢂ (ꢂFor two conformational isomers).13C NMR (CDCl3):
1
2
=
d ¼ 14.08 and 14.27 (2 CH3), 49.83 (d, JPC ¼ 123 Hz, C P), 57.78 (d, JPC ¼ 13 Hz,
CH), 62.29 and 62.46 (2 OCH2), 117.15, 121.22, 121.68, 125.75, 133.16, 153.02,
173.89 (7C benzothiazole), 129.46 (2JPC ¼ 12 Hz), 127.61 (d, JPC ¼ 92 Hz), 131.45
1
4
3
2
ꢂ
=
(d, JPC ¼ 3 Hz), 133.18 (d, JPC ¼ 10 Hz), 168.78 (d, JPC ¼ 12 Hz, C O) , 170.56
(d, JPC ¼ 12 Hz, C O). 31P NMR (CDCl3): d 23.06.
3
ꢂ
=
1
Minor isomer (30%). H NMR (CDCl3): d ¼ 1.14 and 1.34 (6H, 2 t,
3JHH ¼ 7 Hz, 2 CH3), 3.35 and 4.01 (4H, 2q JHH ¼ 7 Hz, 2 OCH2), 4.37 (1H, dd,
3
3
3
3JHP ¼ 5 Hz, JHH ¼ 10Hz, P-C-CH), 6.92 (1H, d, JHH ¼ 10Hz, NH), 13C NMR
1
=
(CDCl3): d ¼ 13.56 and 14.06 (2 CH3), 50.03 (d, JPC ¼ 123 Hz, C P), 57,60 (d,
2JPC ¼ 13Hz, CH), 61.95 and 62.37 (2 OCH2), 117.25, 121.20, 121.64, 125.71, 133.29,
153.19, 173.97 (7C benzothiazole), 129.11 (2JPC ¼ 12Hz), 127.89 (d, JPC ¼ 92Hz),
1
131.68 (d, 4JPC ¼ 3 Hz), 133.29 (d, 3JPC ¼ 10Hz), 31P NMR (CDCl3): d 23.19.
N-(Thiazole-2-yl)triphenyl Iminophosphorane (5a)
Yield: 92%; white powder; mp 141–143 ꢁC. IR (KBr) (nmax, cmꢀ1): 1492, 1435,
1306, 1234, 1100. Calcd. for (C21H17N2PS): C, 69.98; H, 4.75; N, 7.77%. Found: C,
69.80; H, 4.90; N, 7.73%. MS (m=z, %): 360 (M, 100). 1H NMR (500 MHz, CDCl3):
3
3
d ¼ 6.39 (1H, d, JHH ¼ 3.8 Hz, CH of C3H2NS), 6.95 (1H, d, JHH ¼ 3.8 Hz, CH of
C3H2NS,) 7.43–7.83 (15H, m, 3C6H5) ppm. 13C NMR (125.8 MHz, CDCl3):
d ¼ 109.26, 138.99, 174.36 (3C C3H2NS), 129.05 (2JPC ¼ 12 Hz), 129.28 (d, JPC
¼
1
100 Hz), 132.60 (d, JPC ¼ 3 Hz), 133.52 (d, JPC ¼ 10 Hz). 31P NMR (CDCl3):
4
3
=
15.58 (Ph3P N) ppm.
N-(Benzothiazole-2-yl)triphenyl Iminophosphorane (5b)
Yield: 90%; white powder; mp 158–160 ꢁC. IR (KBr) (nmax, cmꢀ1): 1591, 1494,
1438, 1298, 1210, 1106. Calcd. for (C25H19N2PS): C, 73.15; H, 4.67; N, 6.82%. Found:
1
C, 73.30; H, 4.75; N, 6.80%. MS (m=z, %): 410 (M, 100). H NMR (500 MHZ,
CDCl3): d ¼ 6.97–7.40 (4H, m, 4CH), 7.45–7.89 (15H, m, 3C6H5) ppm.13C NMR
(125.8 MHZ, CDCl3): d ¼ 119.12, 120.83, 121.24, 125.19, 134.49, 153.38, 171.75
1
(7C benzothiazole), 129.11 (2JPC ¼ 12 Hz), 128.52 (d, JPC ¼ 100 Hz), 132.83 (d,
4
3
31
=
JPC ¼ 3 Hz), 133.68 (d, JPC ¼ 10 Hz). P NMR (CDCl3): d 15.19 (Ph3P N) ppm.
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