3-(6-Methyl-2-pyrid­yl)-2-phen­oxy-3,4-dihydro-1,3,2-benzoxaza­phosphirine 2-oxide

Rajni Kant; Sabeta Kohli; Lovely Sarmal; M Krishnaiah; V H H Surendra Babu

doi:10.1107/S1600536809029018

. 2009 Jul 25;65(Pt 8):o2003. doi: 10.1107/S1600536809029018

3-(6-Methyl-2-pyridyl)-2-phenoxy-3,4-dihydro-1,3,2-benzoxazaphosphirine 2-oxide

Rajni Kant ^a,^*, Sabeta Kohli ^a, Lovely Sarmal ^a, M Krishnaiah ^b, V H H Surendra Babu ^b

PMCID: PMC2977249 PMID: 21583674

Abstract

In the title compound, C₁₉H₁₇N₂O₃P, the six-membered 1,3,2-oxazaphosphorine ring adopts a twist-boat conformation with the phosphoryl O atom in an equatorial position. The P=O(oxide) bond length is 1.457 (1) Å and the average value of the P—O distances is 1.588 Å. The crystal structure is stabilized by C—H⋯O and C—H⋯π interactions.

Related literature

For the chemistry of organophosphorus heterocyclic compounds, see: Przybylski et al. (1977 ▶); Riffel et al. (1984 ▶); Kleemann & Fluck (1985 ▶); Bettemann et al. (1987 ▶); He et al. (1998 ▶).

Experimental

Crystal data

C₁₉H₁₇N₂O₃P
M _r = 352.33
Monoclinic,
a = 9.2852 (7) Å
b = 14.2972 (11) Å
c = 13.3446 (8) Å
β = 104.545 (7)°
V = 1714.8 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 293 K
0.30 × 0.24 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur diffractometer
Absorption correction: none
14565 measured reflections
4922 independent reflections
4064 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.149
S = 1.08
4922 reflections
227 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: CrysAlis Pro (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis Pro; data reduction: CrysAlis RED (Oxford Diffraction, 2007 ▶); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029018/jh2088sup1.cif

e-65-o2003-sup1.cif^{(17KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029018/jh2088Isup2.hkl

e-65-o2003-Isup2.hkl^{(236.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O3ⁱ	0.93	2.57	3.497 (3)	174
C9—H9⋯O2ⁱ	0.93	2.82	3.706 (2)	159
C7—H7A⋯O3ⁱ	0.97	2.85	3.425 (2)	119
C3—H3⋯O1ⁱⁱ	0.93	2.81	3.373 (3)	120
C11—H11⋯O3ⁱⁱⁱ	0.93	2.66	3.561 (2)	165
C6—H6C⋯O2^iv	0.96	2.81	3.443 (3)	124
C18—H18⋯N2^iv	0.93	2.92	3.818 (5)	163
C10—H10⋯Cg2ⁱⁱⁱ	0.93	2.78	3.437 (2)	128

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) . Cg2 is the centroid of the N1,C1–C5 ring.

Acknowledgments

The authors are grateful to the Department of Science and Technology of the Government of India for funding under research project SR/S2/CMP-47/2003.

supplementary crystallographic information

Comment

Organophosphorus heterocycle compounds containing O and N in a six membered ring have gained much attention because of anti-cancer, anti-tumor and their most significant biological activities as pesticides and drugs(Riffel et al.1984, Kleemann et al.1985, Bettemann et al. 1987, He et al.1998).).

Various compounds of this class viz. cyclophosphamide(2-bis(2-chloroethyl)amino tetrahydro-2H-1,3,2-oxazaphosphorine 2-oxide),ifosfamide(3-(2-chloroethyl)-2-(2-chloroethylamino)tetrahydro-2H-1,3,1-oxazaphosphorine2-oxide) and trofosfamide(3-(2-chloroethyl)-2-(bis(2-chloroethyl)amino)tetrahydro-2H-1,3,2oxazaphosphorine2-oxide) act as antitumor agents (Przybylski et al.,1977).

Because of these significant properties of organophosphorus heterocycle compounds a new compound of this class, i.e., 3-(6-methyl-pyrindin-2-yl)-2-phenoxy-3, 4-dihydrobenzo[e][1,3,2]oxazaphosphirine 2-oxide[I] has been synthesized and its crystal structure is reported here.

In the title compound, [C₁₉H₁₇ N₂O₃ P], the six membered oxazaphosphorine ring adopts a twist boat conformation with phosphoryl oxygen atom at equatorial position. The PO(3) bond length is 1.457 (1)Å and the average value of P—O distance is 1.588 Å. The crystal structure is stabilized by C—H···O and C—H···Π interactions.

Experimental

The title compound was synthesized by adding a solution of phenylphosphorodichloridate (0.002 mole) in 25 ml of dry tetrahydrofuran dropwise over a period of twenty minutes to a stirred solution of 2-{[(6-methyl-2-pyridyl)amino]methyl}phenol (0.002 mole) and triethylamine (0.004 mole) in 30 ml of dry tetrahydrofuran at 0°C. After completion of the addition, the temperature of the reaction mixture was slowly raised to room temperature and stirred for 30 min. Later the reaction mixture was heated to 45–50°C and maintained at that temperature for three hours with stirring. Completion of the reaction was monitored by TLC analysis. Triethylamine- hydrochloride was separated from the reaction mixture by filtration and the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica gel (100–200 mesh) as adsorbent and ethyl acetate:hexane as eluent to afford pure product. Suitable colourless transparent rectangular crystals were obtained from 2-propanol by slow evaporation technique.