Mendeleev Commun., 2019, 29, 153–154
3
7
''
acids with thionyl chloride ). The phosphorylation reactions
were carried out with 1.1 equiv. of phosphinic chloride in the
presence of 1.2 equiv. of triethylamine in toluene. In case of
2 Z. Rádai, P. Szeles, N. Z. Kiss, L. Hegedus, T. Windt, V. Nagy and
G. Keglevich, Heteroatom Chem., 2018, 29, e21436.
3
4
D. Green, S. Elgendy, G. Patel, E. Skordalakes, C. A. Goodwin, M. F.
Scully, V. V. Kakkar and J. J. Deadman, Phosphorus Sulfur Silicon
Relat. Elem., 2000, 156, 151.
H.-W. He, J.-L.Yuan, H. Peng, T. Chen, P. Shen, S.-Q. Wan,Y. Li, H.-L. Tan
Y.-H. He, J.-B. He and Y. Li, J. Agric. Food Chem., 2011, 59, 4801.
5 T. Chen, P. Shen,Y. Li and H.-W. He, J. Fluorine Chem., 2006, 127, 291.
1
-chloro-3-phospholene 1-oxides 2b and 2c, the mixture was
stirred at 25°C for 24 h, while with diphenylphosphinic chloride
a the reaction was complete within 48 h. Compounds 2–4 were
purified by column chromatography and isolated in yields of
6–80%. In case of (1-aryl-1-hydroxymethyl)phosphonates with
chloro or nitro substituent in the aromatic ring (1c and 1d)
somewhat higher yields (51–80%) were attained, as compared
with those starting from the tolyl-substituted hydroxy phosphonate
,
2
6
Q. Long, X. Deng, Y. Gao, H. Xie, H. Peng and H. He, Phosphorus
4
Sulfur Silicon Relat. Elem., 2013, 188, 819.
7
8
L. Meng, R. Joshi, M. Li and H. He, J. Nepal Chem. Soc., 2009, 23, 11.
H. Peng, Q. Long, X. Deng and H. He, Phosphorus Sulfur Silicon Relat.
Elem., 2013, 188, 1874.
1b (46–50%).
9
W. Wang, H.-W. He, N. Zuo, X. Zhang, J.-S. Lin, W. Chen and H. Peng,
The reaction of (1-aryl-1-hydroxymethyl)phosphonates 1a and
c with diphenyl chloridophosphate 4 (Scheme 2) gave the desired
J. Fluorine Chem., 2012, 142, 24.
0 W. Wang, H.-W. He, N. Zuo, H.-F. He, H. Peng and X.-S. Tan, J. Agric.
Food Chem., 2012, 60, 7581.
1 T. Wang, W. Wang, H. Peng and H.-W. He, Chem. Res. Chin. Univ.,
†
1
1
1
1
phosphoryloxy phosphonates 5a and 5b in modest yields of ~16%
after purification by column chromatography, which can be caused
by the lower reactivity of the phosphorylating agent, and the
sensitivity of the products towards moisture. Heating the reaction
mixture did not improve the yields, resulting in the decomposition
of the product.
2
013, 29, 690.
2 W. Wang, Y. Zhou, H. Peng, H.-W. He and X.-T. Lu, J. Fluorine Chem.,
017, 193, 8.
13 X.-B. Chen and D.-Q. Shi, Phosphorus Sulfur Silicon Relat. Elem.,
008, 183, 1134.
2
2
1
4 W. Wang, L.-P. Wang, B.-K. Ning, M.-Z. Mao, C. Xue and H.-Y. Wang,
Phosphorus Sulfur Silicon Relat. Elem., 2016, 191, 1362.
5 J. Yang, J. Ma, W. Che, M. Li, G. Li and B. Song, Chin. J. Org. Chem.,
PhO
PhO
O
O
1
P
2
014, 34, 2566.
PhO
PhO
O
i
16 T. Wang and H.-W. He, Synth. Commun., 2004, 34, 1415.
7 H. Firouzabadi, N. Iranpoor, S. Sobhani and Z. Amoozgar, Synthesis,
P
OMe
OMe
1
a,c
+
1
1
1
Cl
Ar
P
2004, 2, 295.
4
O
8 H. Firouzabadi, N. Iranpoor and S. Farahi, J. Mol. Catal. A: Chem., 2008,
289, 61.
9 H. Firouzabadi, N. Iranpoor, S. Sobhani and Z. Amoozgar, Synthesis,
5
5
a Ar = Ph (15%)
b Ar = 4-ClC6H4 (17%)
2
004, 11, 1771.
20 C. Jin and H. He, Phosphorus Sulfur Silicon Relat. Elem., 2011, 186,
397.
Scheme 2 Conditions: i, Et N, PhMe, 26°C, 72 h.
3
1
2
2
2
1 N. Iranpoor, H. Firouzabadi and D. Khalili, Phosphorus Sulfur Silicon
Relat. Elem., 2011, 186, 2166.
2 L. Xu, G. You, H. Peng and H. He, Phosphorus Sulfur Silicon Relat.
Elem., 2014, 189, 812.
3 B. Kaboudin, S. Emadi, M. R. Faghihi, M. Fallahi and V. Sheikh-Hasani,
J. Enzyme Inhib. Med. Chem., 2013, 28, 576.
New compounds 3 and 5 obtained by the phosphinoylation and
phosphorylation of (1-aryl-1-hydroxymethyl)phosphonates 1 were
3
1
13
1
identified by P, C and H NMR, as well as by HRMS data.
31
1
In the P{ H} NMR spectra of compounds 3a,c,d,f,g,i,j,l, signals
3
of the phosphorus atoms appeared as doublets due to the J
P,P
coupling [Figure S1(a), see Online Supplementary Materials].
Derivatives 3b,e,h,k containing the 3-methyl-3-phospholene
24 J.-P. Li, J.-G. Zhu, R.-J. Liu, F.-L. Cui, P. Liu and G.-S. Liu, S. Afr. J.
Chem., 2008, 61, 5.
2
2
2
5 X. Creary, C. C. Geiger and K. Hilton, J. Am. Chem. Soc., 1983, 105,
851.
6 Z.-G. Li, H.-K. Sun, Q.-M. Wang and R.-Q. Huang, Heteroatom Chem.,
003, 14, 384.
1
-oxide moiety exhibited two sets of doublets resulting from the
presence of two diastereomers due to the two chirality centers
Figure S1(b)]. The same phenomenon was observed in their
2
[
2
1
3
C NMR spectra. The phospholene carbon atoms resonate as
7 L. Hu, S. Lu, F. Yang, J. Feng, Z. Liu, H. Xu and H. He, Phosphorus
doublets due to their coupling with the P atom and the duplica-
tion of signals is referred to the presence of the diastereomers
Sulfur Silicon Relat. Elem., 2002, 177, 2785.
8 D.-L. Kong, G.-Z. Li and R.-D. Liu, Asian J. Chem., 2014, 26, 2138.
9 R. S. Davidson, R. A. Sheldon and S. Trippett, J. Chem. Soc. C, 1967,
2
2
(Figure S2).
1
547.
In summary, a new series of >P(O)OCHP(O)< derivatives has
3
3
0 R. Ruel, J.-P. Bouvier and R. N. Young, J. Org. Chem., 1995, 60, 5209.
1 A. Grün, I. G. Molnár, B. Bertók, I. Greiner and G. Keglevich, Heteroatom
Chem., 2009, 20, 350.
been synthesized by the phosphorylation of (1-aryl-1-hydroxy-
methyl)phosphonates with P-chlorides. The new compounds are
of potential biological activity.
32 G. Keglevich, A. Grün, I. G. Molnár and I. Greiner, Heteroatom Chem.,
2
011, 22, 640.
3
3
3
3 E. Årstad and L. Skattebøl, Tetrahedron Lett., 2002, 43, 8711.
4 J. Zhou, R. Chen and X. Yang, Heteroatom Chem., 1998, 9, 369.
5 N. Z. Kiss,A. Simon, L. Drahos, K. Huben, S. Jankowski and G. Keglevich,
Synthesis, 2013, 45, 199.
This work was supported by the National Research Develop-
ment and Innovation Fund (K119202). Z. Rádai was supported by
the New National Excellence Program of the Ministry of Human
Capacities (ÚNKP-18-3-IV-BME-265) and acknowledges the
fellowship provided by Chinon–Sanofi Pharmaceuticals and
József Varga Foundation.
3
6 G. Keglevich, Z. Rádai and N. Z. Kiss, Green Process Synth., 2017,
6, 197.
3
7 G. Keglevich, I. Petneházy, P. Miklós, A. Almásy, G. Tóth, L. To'' ke and
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Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi: 10.1016/j.mencom.2019.03.011.
References
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Received: 10th September 2018; Com. 18/5687
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