Three-component reaction between triphenylphosphine, dialkyl acetylenedicarboxylate and 4-amino-5-alkyl-2,4-dihydro-1,2,4-triazole-3-thiones: An efficient one-pot synthesis of stable phosphorus ylides

Article abstract of DOI:10.1080/17415991003682617

Protonation of the reactive 1:1 intermediate produced in the reaction between dialkyl acetylenedicarboxylates and triphenylphosphine by 4-amino-5-alkyl-2,4-dihydro-1,2,4-triazole-3-thione leads to vinylphosphonium salts which undergo Michael addition with

Full text of DOI:10.1080/17415991003682617

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Three-component reaction between
triphenylphosphine, dialkyl
acetylenedicarboxylate and 4-amino-5-
alkyl-2,4-dihydro-1,2,4-triazole-3-
thiones: an efficient one-pot synthesis
of stable phosphorus ylides
Mohammad Hossein Mosslemin a , Mohammad Anary-Abbasinejad a
, Alireza Hassanabadi b & Mohammad Ali Bagheri a
a Department of Chemistry , Islamic Azad University , Yazd
Branch, PO Box 89195-155, Yazd, Iran
b Department of Chemistry , Islamic Azad University , Zahedan
Branch, Zahedan, Iran
Published online: 07 Apr 2010.
To cite this article: Mohammad Hossein Mosslemin , Mohammad Anary-Abbasinejad ,
Alireza Hassanabadi & Mohammad Ali Bagheri (2010) Three-component reaction between
triphenylphosphine, dialkyl acetylenedicarboxylate and 4-amino-5-alkyl-2,4-dihydro-1,2,4-
triazole-3-thiones: an efficient one-pot synthesis of stable phosphorus ylides, Journal of Sulfur
Chemistry, 31:2, 135-139, DOI: 10.1080/17415991003682617
To link to this article: http://dx.doi.org/10.1080/17415991003682617
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Journal of Sulfur Chemistry
Vol. 31, No. 2, April 2010, 135–139
Three-component reaction between triphenylphosphine, dialkyl
acetylenedicarboxylate and 4-amino-5-alkyl-2,4-dihydro-1,2,
4-triazole-3-thiones: an efficient one-pot synthesis of stable
phosphorus ylides
Mohammad Hossein Mosslemina*, Mohammad Anary-Abbasinejada, Alireza Hassanabadib
and Mohammad Ali Bagheria
aDepartment of Chemistry, Islamic Azad University, Yazd Branch, PO Box 89195-155, Yazd, Iran;
bDepartment of Chemistry, Islamic Azad University, Zahedan Branch, Zahedan, Iran
(Received 8 January 2010; final version received 7 February 2010)
Protonation of the reactive 1:1 intermediate produced in the reaction between dialkyl acetylenedicarboxy-
lates and triphenylphosphine by 4-amino-5-alkyl-2,4-dihydro-1,2,4-triazole-3-thione leads to vinylphos-
phonium salts which undergo Michael addition with the conjugate base of the NH-acid to produce highly
functionalized, salt-free phosphorus ylides in excellent yields.
Keywords: addition reaction; dialkyl acetylenedicarboxylates; phosphorus ylides; triphenylphosphine;
NH-acid
1. Introduction
Organophosphorus compounds, those bearing a carbon atom bound directly to a phosphorus atom,
are synthetic targets of interest, at least because of their value for a variety of industrial, biological,
and chemical synthetic uses (1–3). Several methods have been developed for the preparation of
phosphorus ylides. These ylides are usually prepared by treatment of an appropriate phosphonium
salt with a base; the corresponding phosphonium salts are usually obtained from the phosphine and
an alkyl halide (1, 2). Phosphonium salts are also prepared by the Michael addition of phosphorus
nucleophiles to activated olefins (1, 2). Reaction of acetylenic esters with triphenylphosphine in
the presence of an organic compound possessing an acidic hydrogen has been recently reported
to produce phosphorus ylides (4–12). In continuation of our works on the reaction between
triphenylphosphine and acetylene diesters in the presence of organic N–H, O–H or C–H acids
(13a–f ), we herein report an efficient synthetic route to stable phosphorus ylides using three-
component reaction between dialkyl acetylenedicarboxylates (DAADs), triphenylphosphine and
4-amino-5-alkyl-2,4-dihydro-1,2,4-triazole-3-thione (2).
*Corresponding author. Email: mhmosslemin@yahoo.com
ISSN 1741-5993 print/ISSN 1741-6000 online
© 2010 Taylor & Francis
DOI: 10.1080/17415991003682617
http://www.informaworld.com

136 M.H. Mosslemin et al.
2. Results and discussion
The reaction of the 4-amino-5-alkyl-2,4-dihydro-1,2,4-triazole-3-thione (2) with DAAD (3) in the
presence of triphenylphosphine 1 leads to the corresponding ylide 4 in good yields (Scheme 1).The
1H NMR spectrum of compound 4a displays two sharp singlets (δ3.13, 3.71 ppm) for the protons
of two methoxy groups, a doubled signal for the methine proton at 5.43 ppm (3JHP = 16 Hz)
and multiplets between 7.26 and 7.72 ppm for aromatic protons. A broad singlet was observed
at 1.69 ppm that disappeared after the addition of a few drops of D2O to CDCl3 solution of
compound 4a. This signal is related to NH2 protons. The 13C NMR spectrum of compound 4a
showed13distinctsignals, whichisconsistentwiththeproposedstructure.The 31PNMRspectrum
of compound 4a consists of one signal at 23.2 ppm. This shift is similar to those observed for
other stable phosphorus ylides (14, 15). The structural assignments made on the basis of the NMR
spectra of compounds 4a–f are supported by their IR spectra. The carbonyl region of the spectrum
exhibits absorption bands at 1750 cm−1 for the ester groups and at 3300 and 3460 cm−1 for the
NH2 group.
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 triazole. The positively
charged ion 5 is then attacked by the triazole anion 6 to form 4 (Scheme 2).
In summary, we report herein that the three-component reaction between DAADs and triph-
enylphosphine by 4-amino-5-alkyl-2,4-dihydro-1,2,4-triazole-3-thiones produces functionalized
phosphorus ylides in good yields. The advantages of the reported method are simple available
Scheme 1. Three-component reaction between triphenylphosphine, DAADs and 4-amino-5-
alkyl-2,4-dihydro-1,2,4-triazole-3-thiones.
Scheme 2. Suggested mechanism for formation of ylides 4.

Journal of Sulfur Chemistry 137
starting materials, short reaction time, simple work-up, neutral reaction conditions and high
yields.
3. Experimental
All melting points are uncorrected. Elemental analyses were performed at the Analytical Labo-
ratory of Islamic Azad University, Yazd Branch, using a Costech ECS 4010 CHNS-O analyzer.
Mass spectra were recorded on a FINNIGAN-MAT 8430 mass spectrometer operating at an ion-
ization potential of 70 eV. IR spectra were recorded on a Shimadzu IR-470 spectrometer. 1H, 13
C
and 31P NMR spectra were recorded on a BRUKER DRX-500 AVANCE spectrometer at 500,
128.5 and 202.5 MHz, respectively. 1H, 13C and 31P NMR spectra were obtained on a solution in
CDCl3 using TMS as the internal standard or 85% H3PO4 as the external standard. The chemicals
used in this work were purchased from Fluka (Buchs, Switzerland) and were used without further
purification.
3.1. General procedure
A magnetically stirred solution of triphenylphosphine (2 mmol) and 4-amino-5-alkyl-2,4-dihydro-
1,2,4-triazole-3-thione (2 mmol) in DMF (10 mL) was added dropwise to a mixture of DAAD
(2 mmol) in DMF (3 mL) at room temperature for 2 min. The reaction mixture was then stirred
for 1 h. Water (50 mL) was added and the solid was filtered off and washed with diethyl ether to
give the pure product.
3.2. Dimethyl 2-(4-amino-5-methyl-4H-1,2,4-triazol-3-yl-sulfanyl)-3-(triphenyl-λ5-
phosphanylidene)-succinate (4a)
White powder; yield: 93%; m.p. 160–162◦C. IR (KBr) (νmax, cm−1): 1750 (C O), 3300, 3460
=
(NH2). Analyses: Calcd. for C27H27N4O4PS: C, 60.66; H, 5.09; N, 10.48. Found: C, 60.4; H, 5.2;
N, 10.6. MS (m/z, %): 534 (M+, 7).
1H NMR (500.1 MHz, CDCl3): δ1.69 (2H, s, NH2), 2.40 (3H, s, CH3), 3.13 (3H, s, OCH3), 3.71
(3H, s, OCH3), 5.43 (1H, d, 3JPH = 16 Hz), 7.26–7.72 (15H, m, aromatic). 13C NMR (125.8 MHz,
2
CDCl3): δ9.8 (CH3), 48.3 (OCH3), 50.5 (d, 1JPC = 126 Hz,C P), 51.7 (OCH3), 61.5 (d, JPC
=
=
16 Hz, CH), 125.3 (d, JPC = 94 Hz), 127.8 (2JPC = 12 Hz), 132.1 (d, JPC = 2 Hz), 132.8 (d,
1
4
3
2
3
=
=
=
JPC = 10 Hz), 146.9 (SC N), 164.6 (NC N), 169.5 (d, JPC = 12 Hz C O), 171.3 (d, JPC
=
17 Hz C O). 31P NMR (202.5 MHz, CDCl3): δ22.82.
=
3.3. Diethyl 2-(4-amino-5-methyl-4H-1,2,4-triazol-3-yl-sulfanyl)-3-(triphenyl-λ5-
phosphanylidene)-succinate (4b)
White powder; yield: 92%; m.p. 152–154◦C. IR (KBr) (νmax, cm−1): 1748 (C O), 3295, 3485
(NH2). Analyses: Calcd. for C29H31N4O4PS: C, 61.91; H, 5.55; N, 9.96. Found: C, 61.7; H, 5.4;
N, 10.2. MS (m/z, %): 562 (M+, 6).
=
1H NMR (500.1 MHz, CDCl3): δ0.43 (3H, t, JHH = 7 Hz, CH3), 1.15 (3H, t, JHH = 7 Hz,
3
3
3
CH3), 1.70 (2H, s, NH2), 1.94 (3H, s, CH3), 3.65 (2H, d, JHH = 7 Hz, OCH2), 3.77 (2H, d,
3
3JHH = 7 Hz, OCH2), 5.44 (1H, d, JPH = 16 Hz), 7.26–7.73 (15H, m, aromatic). 13C NMR
(125.8 MHz, CDCl3): δ11.3 (CH3), 13.9 and 14.2 (2CH3), 41.3 (d, 1JPC = 122 Hz, C P), 57.9
=
(d, 2JPC = 15 Hz, CH), 61.7 and 62.6 (2 OCH2), 126.1 (d, 1JPC = 91 Hz), 128.8 (2JPC = 12 Hz),
2
132.1 (d, 4JPC = 2 Hz), 133.7 (d, 3JPC = 10 Hz), 147.3 (SC N), 165.4 (NC N), 169.8 (d, JPC
=
=
=
3
12 Hz C O), 170.9 (d, JPC = 18 Hz C O). 31P NMR (202.5 MHz, CDCl3): δ22.97.
=
=

138 M.H. Mosslemin et al.
3.4. Di-t-butyl 2-(4-amino-5-methyl-4H-1,2,4-triazol-3-yl-sulfanyl)-3-(triphenyl-λ5-
phosphanylidene)-succinate (4c)
White powder; yield: 97%; m.p. 165–167◦C. IR (KBr) (νmax, cm−1): 1744 (C O), 3395, 3525
=
(NH2). Analyses: Calcd. for C33H39N4O4PS: C, 64.06; H, 6.35; N, 9.06. Found: C, 63.9; H, 6.5;
N, 9.2. MS (m/z, %): 618 (M+, 9).
1H NMR (500.1 MHz, CDCl3): δ0.83 (9H, s, t-Bu), 1.42 (9H, s, t-Bu), 1.45 (2H, s, NH2), 2.32
(3H, s, CH3), 5.43 (1H, d, 3JPH = 16 Hz), 7.28-7.97 (15H, m, aromatic). 13C NMR (125.8 MHz,
1
=
CDCl3): δ11.3(CH3), 28.7 and 28.9 (6 CH3 of 2 t-Bu), 55.0 (d, JPC = 126 Hz, C P), 63.4
2
1
(d, JPC = 16 Hz, CH), 76.7 and 80.5 (2 O-C(CH3)3), 127.9 (d, JPC = 94 Hz), 129.5 (2JPC
=
12 Hz), 132.9 (d, 4JPC = 2 Hz), 134.1 (d, 3JPC = 10 Hz), 147.2 (SC N), 163.2 (NC N), 169.5
=
=
(d, 2JPC = 12 Hz C O), 171.3 (d, JPC = 17 Hz C O). 31P NMR (202.5 MHz, CDCl3): δ22.78.
3
=
=
3.5. Dimethyl 2-(4-amino-5-ethyl-4H-1,2,4-triazol-3-yl-sulfanyl)-3-(triphenyl-λ5-
phosphanylidene)-succinate (4d)
White powder; yield: 95%; m.p. 124–126◦C. IR (KBr) (νmax, cm−1): 1751 (C O), 3265, 3540
=
(NH2). Analyses: Calcd. for C28H29N4O4PS: C, 61.30; H, 5.33; N, 10.21. Found: C, 61.5; H, 5.1;
N, 10.4. MS (m/z, %): 548 (M+, 4).
1H NMR (500.1 MHz, CDCl3): δ 1.31 (3H, t, 3JHH = 7HZ, CH3), 1.62 (2H, s, NH2), 2.78 (2H,
3
3
q, JHH = 7 Hz, CH2), 3.13 (3H, s, OCH3), 3.72 (3H, s, OCH3), 5.56 (1H, d, JPH = 16 Hz,),
7.34–7.72 (15H, m, aromatic). 13C NMR (125.8 MHz, CDCl3): δ10.6 (CH3), 18.5 (CH2), 49.8
1
2
=
(d, JPC = 126 Hz, C P), 52.4 (OCH3), 52.6 (OCH3), 62.7 (d, JPC = 16 Hz, CH), 125.9 (d,
1JPC = 94 Hz), 128.6 (2JPC = 12 Hz), 132.0 (d, JPC = 2 Hz), 133.7 (d, JPC = 10 Hz), 151.3
4
3
(SC N), 165.9 (NC N), 169.8 (d, JPC = 12 Hz C O), 170.1 (d, JPC = 17 Hz, C O). 31P
2
3
=
=
=
=
NMR (202.5 MHz, CDCl3): δ22.75.
3.6. Diethyl 2-(4-amino-5-ethyl-4H-1,2,4-triazol-3-yl-sulfanyl)-3-(triphenyl-λ5-
phosphanylidene)-succinate (4e)
White powder; yield: 93%; m.p. 113–115◦C. IR (KBr) (νmax, cm−1): 1749 (C O), 3280, 3535
=
(NH2). Analyses: Calcd. for C30H33N4O4PS: C, 62.49; H, 5.77; N, 9.72. Found: C, 62.6; H, 5.6;
N, 9.9. MS (m/z, %): 576 (M+, 7).
3
3
1H NMR (500.1 MHz, CDCl3): δ0.45 (3H, t, JHH = 7 Hz, CH3), 1.16 (3H, t, JHH = 7 Hz,
3
CH3), 1.32 (3H, s, CH3), 1.73 (2H, s, NH2), 2.77 (2H, d, JHH = 7 Hz, CH2), 3.78 (2H, d,
3JHH = 7 Hz, OCH2), 4.08 (2H, d, 3JHH = 7 Hz, OCH2), 5.62 (1H, d, 3JPH = 16 Hz,CH), 7.31–
7.62(15H, m, aromatic). 13C NMR(125.8 MHz, CDCl3):δ10.5(CH3), 13.9and14.2(2CH3), 18.5
(CH2), 39.3 (d, 1JPC = 122 Hz, C P), 57.8 (d, JPC = 15 Hz, CH), 61.4 and62.9 (2 OCH2), 126.5
2
=
1
2
4
3
(d, JPC = 91 Hz), 128.7 (d, JPC = 12 Hz), 132.0 (d, JPC = 2 Hz), 133.8 (d, JPC = 10 Hz),
2
3
=
=
=
=
151.3 (SC N), 165.9 (NC N), 169.7 (d, JPC = 12 Hz, C O), 171.0 (d, JPC = 18 Hz, C O).
31P NMR (202.5 MHz, CDCl3): δ22.81.
3.7. Di-t-butyl 2-(4-amino-5-ethyl-4H-1,2,4-triazol-3-yl-sulfanyl)-3-(triphenyl-λ5
-phosphanylidene)-succinate (4f)
White powder; yield: 95%; m.p. 165–167◦C. IR (KBr) (νmax, cm−1): 1746 (C O), 3390, 3517
=
(NH2). Analyses: Calcd. for C34H41N4O4PS: C, 64.54; H, 6.53; N, 8.85. Found: C, 64.7; H, 6.7;
N, 8.9.MS (m/z, %): 632 (M+, 6).

Journal of Sulfur Chemistry 139
3
1H NMR (500.1 MHz, CDCl3): δ0.81 (9H, s, t-Bu), 1.29 (3H, t, JHH = 7 Hz, CH3), 1.40
(9H, s, t-Bu), 1.52 (2H, s, NH2), 2.73 (2H, q, 3JHH = 7 Hz, CH2), 5.49 (1H, d, 3JPH = 16 Hz),
7.32–7.91 (15H, m, aromatic). 13C NMR (125.8 MHz, CDCl3): δ10.3 (CH3), 18.6 (CH2), 28.2
and 28.7 (6 CH3 of 2 t-Bu), 55.2 (d, 1JPC = 126 Hz, C P), 62.8 (d, JPC = 16 Hz, CH), 76.4 and
2
=
80.7 (2 O–C(CH3)3), 127.3 (d, JPC = 94 Hz), 129.4 (2JPC = 12 Hz), 132.7 (d, JPC = 2 Hz),
1
4
133.8 (d, 3JPC = 10 Hz), 147.0 (SC N), 162.9 (NC N), 169.7 (d, JPC = 12 Hz, C O), 171.1
2
=
=
=
(d, 3JPC = 17 Hz, C O). 31P NMR (202.5 MHz, CDCl3): δ 22.65.
=
Acknowledgements
We gratefully acknowledge the financial support from the Research Council of Islamic Azad University of Yazd and The
Islamic Azad University of Zahedan of Iran.
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