A novel route to spiro phosphorus-heterocycle via Lawesson's reagent

Article abstract of DOI:10.1081/SCC-120003639

2-Aryl-spiro-[5,5]-1,3,2-dioxaphosphorinane-2-sufides were prepared by the cyclization reaction of Lawesson's reagent with pentaerythritol and monobenzalpentaerythritol, respectively.

Full text of DOI:10.1081/SCC-120003639

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A NOVEL ROUTE TO SPIRO PHOSPHORUS-HETEROCYCLE
VIA LAWESSON'S REAGENT
Liangnian He a , Yanping Luo a c , Kai Li a , Mingwu Ding a , Aihong Lu a , Xiaopeng Liu b ,
Tianjie Wu b & Fei Cai b
a Institute of Organic Synthesis , Central China Normal University , Wuhan, 430079, P.R.
China
b Center of Analysis and Testing , Central China Normal University , Wuhan, 430079, P.R.
China
c College of Plant Protection , South China University of Tropical Agriculture , Danzhou,
Hainan, 571737, P.R. China
Published online: 17 Aug 2006.
To cite this article: Liangnian He , Yanping Luo , Kai Li , Mingwu Ding , Aihong Lu , Xiaopeng Liu , Tianjie Wu & Fei Cai (2002)
A NOVEL ROUTE TO SPIRO PHOSPHORUS-HETEROCYCLE VIA LAWESSON'S REAGENT, Synthetic Communications: An International
Journal for Rapid Communication of Synthetic Organic Chemistry, 32:9, 1415-1419, DOI: 10.1081/SCC-120003639
To link to this article: http://dx.doi.org/10.1081/SCC-120003639
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SYNTHETIC COMMUNICATIONS, 32(9), 1415–1419 (2002)
A NOVEL ROUTE TO SPIRO
PHOSPHORUS-HETEROCYCLE VIA
LAWESSON’S REAGENT
Liangnian He,1, Yanping Luo,1,3 Kai Li,1
*
Mingwu Ding,1 Aihong Lu,1 Xiaopeng Liu,2
Tianjie Wu,2 and Fei Cai2
1Institute of Organic Synthesis, Central China
Normal University, Wuhan 430079, P.R. China
2Center of Analysis and Testing, Central China
Normal University, Wuhan 430079, P.R. China
3College of Plant Protection,
South China University of Tropical Agriculture,
Danzhou, Hainan 571737, P.R. China
ABSTRACT
2-Aryl-spiro-[5,5]-1,3,2-dioxaphosphorinane-2-sufides were
prepared by the cyclization reaction of Lawesson’s
reagent with pentaerythritol and monobenzalpentaerythritol,
respectively.
Key Words: Cyclization; Lawesson’s reagent; Pentaerythri-
tol; Spiro phosphorus heterocycle
*Corresponding author. Current address: Molecular Catalysis Group, Department
of Molecular Engineering, National Institute of Materials and Chemical Research,
1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan. Fax: +81 298 61 4511; E-mail:
helini@nimc.go.jp
1415
Copyright & 2002 by Marcel Dekker, Inc.
www.dekker.com

1416
HE ET AL.
In recent years, our research interest has been focused on the devel-
opment of new synthetic methodology centered around biologically active
phosphorus heterocycles,1 because functionalized phosphorus heterocycles
and their derivatives are bioactive substances of great interest with various
properties.2–6 In the preceding papers,1 we disclosed a methodology to pre-
pare 5-membered and 6-membered phosphorus heterocycles with biological
activity via cyclization of Lawesson’s reagent, 2,4-bis(4-methoxyphenyl)-
1,3,2,4-dithiadiphosphetane-2,4-disulfide, with bifunctional substrates. The
fact that this cyclization reaction is readily applicable to other bifunctional
compounds to form different kinds of phosphorus-heterocycles prompted us
to develop a new method for synthesis of spiro phosphorus-heterocycles.
The preparation of spiro crown ethers and rings are of importance since
their complexes play an important role in biological systems and coordina-
tion chemistry.7 We report here the synthesis of 2-aryl-spiro-[5,5]-1,3,2-diox-
aphosphorinane-2-sufides 3 and 4 starting from pentaerythritol 1 and
monobenzalpentaerythritol 2 using Lawesson’s reagent.
RESULTS AND DISCUSSION
Lawesson’s reagent reacted with pentaerythitol 1 in anhydrous aceto-
nitrile as a solvent using 2.2 : 1 molar ratio at reflux under dry nitrogen for
6–8 h to afford the spiro heterocyles 3 in significant yields, as well as thio-
acetamide (m.p. 113ꢀC) as a side product, as depicted in Scheme 1.
Similarly, 1.1 molar equivalent of Lawesson’s reagent was treated with
monobenzalpentaerythritol 2a–b to provide the ring 4a–b. All new com-
pounds were identified satisfactorily by elemental analyses and spectral
data (IR, NMR, and MS) (Scheme 1).
EXPERIMENTAL
Melting points were determined with a model X4 apparatus and are
1
uncorrected. H NMR spectra and 31P NMR spectra were recorded on a

SPIRO PHOSPHORUS-HETEROCYCLE
1417
Scheme 1.
Varian XL-200 MHz spectrometer. Mass spectra were measured on a HP
5988A spectrometer. Elemental analyses were measured with a PE-2400
elementary analyzer. The IR spectra were measured by using a Shimadzu-
408 instrument. Column chromatography was performed on silica gel II
(10–40 m, Hai Yang Chemical Factory of Qingdao). All solvents and
materials were reagent grade and purified as required. Monobenzalpenta-
erythritol 2a–b were obtained from pentaerythritol and benzaldehyde in the
usual way.8 Lawesson’s reagent was prepared in a yield of 75% according to
published procedure.9
General procedure for synthesis of 3 and 4a–b: A three-necked flask
equipped with a dropping funnel, stirrer, drying CaCl2 tube and nitrogen
gas inlet was charged with 10 ml of anhydrous acetonitrile and 1 mmol of
pentaerythritol 1 or monobenzalpentaerythritol 2a–b. Then Lawesson’s
reagent (2.2 mmol, 1.1 mmol for preparation of 4a–b) was added to the
flask at room temperature. After complete addition, the stirred reaction
mixture was refluxed under dry nitrogen for 6–8 h until no starting materials
could be detected (TLC). Evaporation of the solvent followed by
column chromatography on silica gel (column size: 4 cm in diameter ꢁ 15 cm
cm long; 10 grams of silica gel, Rf ¼ 0.55) using light petroleum ether

1418
HE ET AL.
(b.p. 40–60ꢀC)-dry ethyl ether as eluent yielded the corresponding hetero-
cycles 3 and 4a–b. Yields were determined after separation on silicon gel
column. The structures of the new compounds were confirmed by elemental
analyses and spectral results.
3: m.p. 197–198ꢀC; 0.169g (yield 35.8%); 1H NMR dH (DMSO-d6):
3.84 (s, 6H, 2 ꢁ CH3O), 4.1–4.2 (m, 8H, 4 ꢁ CH2), 7.0–8.0 (m, 8H, aromatic
protons, Ar-H). 31P NMR dP (DMSO-d6): 89.09. IR n (KBr, cmÀ1): 750
(P¼S), 1050 (P-O-C). EI-MS (int. rel) m/z (%): 472 (Mþ, 88). Anals.
calcd for C19H22O6P2S2: C, 48.31; H, 4.66. Found: C, 48.22; H, 4.48.
4a: m.p. 131–132ꢀC; 0.127 g (yield 32.4%); H NMR dH (DMSO-d6):
1
3.87 (s, 3H, CH3O), 4.0–4.2 (m, 8H, 4 ꢁ CH2), 7.0–7.9(m, 9H, aromatic
protons, Ar-H). 31P NMR dP (DMSO-d6): 88.34. IR n (KBr, cmÀ1): 750
(P¼S), 1060 (P-O-C). EI-MS (int. rel) m/z (%): 392 (Mþ, 48). Anals.
calcd for C19H21O5PS: C, 58.16; H, 5.36. Found: C, 58.34; H, 5.12.
4b: m.p. 137–138ꢀC; 0.162 g (yield 38.4%); H NMR dH (DMSO-d6):
1
3.89(s, 6H, 2 ꢁ CH3O), 4.1–4.2 (m, 8H, 4 ꢁ CH2), 7.1–7.8 (m, 8H, aromatic
protons, Ar-H). IR n (KBr, cmÀ1): 760 (P¼S), 1060 (P-O-C). EI-MS (int.
rel) m/z (%): 422 (Mþ, 32). Anals. calcd for C20H23O6PS: C, 56.87; H, 5.45.
Found: C, 56.63; H, 5.61.
ACKNOWLEDGMENT
Thanks are due to the Dawn Plan of Science and Technology for
Young Scientists of Wuhan City and Natural Science Foundation of
Hubei Province for financial support.
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Received in the USA May 14, 2001