2,2,2-Tribromonaphtho[2,3-d]-1,3,2-dioxaphosphole: Obtaining and reaction with phenylacetylene

Article abstract of DOI:10.1080/10426500701795993

The reaction of 2,3-dihydroxynaphthalene with phosphorus tribromide followed by bromide treatment has been shown to lead to quantitative formation of the new 2,2,2 tribromonaphtho [2,3-d]-1,3,2-dioxaphosphole. Its interaction with phenylacetylene proceeds

Full text of DOI:10.1080/10426500701795993

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2,2,2-Tribromonaphtho[2,3-
d]-1,3,2-Dioxaphosphole:
Obtaining and Reaction with
Phenylacetylene
A. V. Bogdanov a , V. F. Mironov a , B. I. Buzykin a , A.
B. Dobrynin a , D. B. Krivolapov a & A. I. Konovalov a
a A.E.Arbuzov Institute of Organic and Physical
Chemistry , Russian Academy of Sciences , Russia
Published online: 20 Jun 2008.
To cite this article: A. V. Bogdanov , V. F. Mironov , B. I. Buzykin , A. B.
Dobrynin , D. B. Krivolapov & A. I. Konovalov (2008) 2,2,2-Tribromonaphtho[2,3-
d]-1,3,2-Dioxaphosphole: Obtaining and Reaction with Phenylacetylene,
Phosphorus, Sulfur, and Silicon and the Related Elements, 183:2-3, 650-651, DOI:
10.1080/10426500701795993
To link to this article: http://dx.doi.org/10.1080/10426500701795993
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Phosphorus, Sulfur, and Silicon, 183:650–651, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701795993
2,2,2-Tribromonaphtho[2,3-d]-1,3,2-Dioxaphosphole:
Obtaining and Reaction with Phenylacetylene
A. V. Bogdanov, V. F. Mironov, B. I. Buzykin, A. B.
Dobrynin, D. B. Krivolapov, and A. I. Konovalov
A.E.Arbuzov Institute of Organic and Physical Chemistry, Russian
Academy of Sciences, Russia
The reaction of 2,3-dihydroxynaphthalene with phosphorus tribromide followed by
bromide treatment has been shown to lead to quantitative formation of the new 2,2,2
tribromonaphtho [2,3-d]-1,3,2-dioxaphosphole. Its interaction with phenylacetylene
proceeds by several pathways and leads to unexpected formation of 2-phenyl-9-
(2-dihydroxyphosphoryl-1-phenylethen-1-yl)naphtho[1,2-d]furane. The structure of
the last compound was established by NMR and single crystal X-ray diffraction.
Keywords 2,3-dihydroxynaphthalenes; phosphorus tribromides; phosphole; phenylace-
hylene; naphthofurane; crystal structure
The interaction of 2,2,2-trichlorobenzo[d]-1,3,2-dioxaphosphole with
arylacetylenes is a versatile approach to the synthesis of benzo[e]-
1,2-oxaphosphorinine derivatives–P-analogues of coumarines.1
Here, we report the obtaining of 2,2,2-tribromonaphtho[2,3-d]-1,3,2-
dioxaphosphole 1 from 1,2-naphthalenediol, PBr3 and bromine and
its reaction with phenylacetylene. The reaction of phosphole 1 with
phenylacetylene proceeds in several directions (10–15◦C) (Scheme 1).
The first and second pathways include the formation of heterocycles
2 (2–3%) and 3 (20–23%) after the reaction mixture hydrolysis. The
third pathway is the disproportionation of the phosphole 1, with the
following bromination resulting in the formation of phosphoranes 4, 5.
The phosphates 6, 7 were obtained as a result of the hydrolysis. We suc-
ceeded in isolation of compound 3, 7. Phosphate 6 was obtained by the
independent synthesis also. The structure of 2-phenyl-9-(2-dihydroxy
phosphoryl-1-phenylethen-1-yl)naphtho[1,2-d]furane 3 was confirmed
by the X-ray single crystal diffraction (Figure 1).
The work is supported by the President of Russian Federation program (MK-
2444.2007.3).
Address correspondence to A. V. Bogdanov, A. E. Arbuzov Institute of Organic and
Physical Chemistry, Russian Academy of Sciences, Russia. E-mail:bogdanov@iopc.knc.ru.
650

2,2,2-Tribromonaphtho[2,3-D]-1,3,2-Dioxaphosphole
651
SCHEME 1
FIGURE 1 The geometry of molecule 3 (solvate with DÃS) in crystal.
REFERENCE
[1] V. F. Mironov, I. A. Litvinov, A. A. Shtyrlina, A. T. Gubaidullin, R. R. Petrov, A. I.
Konovalov, N. M. Azancheev, and R. Z. Musin, Zh. Obshch. Khim. (Rus. J. Gen. Chem.),
70, 1117 (2000).