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Synlett 2006(10): 1613-1615  
DOI: 10.1055/s-2006-944196
LETTER
© Georg Thieme Verlag Stuttgart · New York

Reaction of Non-Racemic (1-Phenyl)ethylamines with Chloromethyl­isothiocyanatothiophosphonates: Synthesis of Optically Active 1,3,4-Thiazaphospholes

Natalia A. Khailova, Roza Kh. Bagautdinova, Olga N. Kataeva, Mikhail A. Pudovik, Vladimir A. Alfonsov*, Arkady N. Pudovik
A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre of the Russian Academy of Sciences, Arbuzov Str. 8, 420088 Kazan, Russian Federation
Fax: +7(8432)732253; e-Mail: alfonsov@iopc.knc.ru;
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Publication History

Received 9 February 2006
Publication Date:
12 June 2006 (online)

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Abstract

Both enantiomers of the major diastereomer of 2-(1-­phenyl)ethylamino-4-thioxo-4-phenoxy-1,3,4-thiazaphosphol-2-ine were obtained in optically pure form by the reaction of O-­phenyl(chloromethyl)isothiophosphonate with (R)-(+)- and (S)-(-)-(1-phenyl)ethylamine.

Key words

organophosphorus compounds - chloromethylisothio­cyanatothiophosphonates - thiazaphospholes - enantiomers

    References and Notes

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  • 4 Kamalov RM. Khailova NA. Gazikasheva AA. Chertanova LF. Pudovik MA. Pudovik AN. Dokl. Akad. Nauk. SSSR  1991,  6:  1406 
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  • 5 Khailova NA. Krepysheva NE. Saakyan GM. Bagautdinova RKh. Shaimardanova AA. Azancheev NM. Litvinov IA. Gubaidullin AT. Zverev VV. Pudovik MA. Pudovik AN. Zh. Obshch. Khim.  2002,  72:  1145 
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  • 8a

    Crystallographic data (excluding structure factors) for the structures in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication numbers CCDC 264300 and 264301. Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK [fax:+44 (1223)336033 or e-mail: deposit@ccdc.cam.ac.uk]

  • 8b

    Data set was collected on an Enraf Nonius CAD4 diffractometer.

  • 8c Programs used: Data collection EXPRESS   Nonius B.V.; Delft: 1994. 
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  • 8d Data reduction and structure solution: Fair K. MolEN   Enraf-Nonius B.V.; Delft: 1990. 
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  • 8e Structure refinement: Sheldrick GM. SHELXL-97   University of Göttingen; Germany: 1997. 
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  • 8f Graphics: Keller E. SCHAKAL-97   University of Freiberg; Germany: 1997. 
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  • 8g

    Formula C16H17N2OPS2, M = 348.41, colorless crystal 0.45 × 0.25 × 0.10 mm, a = 5.682 (4), b = 15.000(10), c = 10.490 (9) Å, β = 105.12 (6)°, V = 863.1 (11) Å3, ρcalc = 1.341 gcm-3, µ = 3.68 cm-1, empirical absorption correction (0.288 < T < 0.709), Z = 2, monoclinic, space group P21 (No. 4), λ = 1.54184 Å, T = 293 K, ω scans, 2402 reflections collected (+h, ±k, ±l), [(sinθ)/λ] = 0.66 Å-1, 1770 independent observed reflections [I - 2 σ(I)] (Rint = 0.041), 200 refined parameters, R = 0.055, wR2 = 0.144, max. residual electron density 0.28 (-0.25) eÅ-3, hydrogen atoms at nitrogen atoms obtained from difference Fourier calculations, others calculated and refined as riding atoms.

6

( R C , S P )-2-(1-Phenyl)ethylamino-4-thioxo-4-phenoxy-1,3,4-thiazaphosphole ( 4b)
To 1 (2.0 g, 7.53 mmol, 1 equiv) in anhyd benzene (25 mL) at 0 °C was added a mixture of Et3N (0.38 g, 3.76 mmol) and 3 (0.46 g, 3.76 mmol, 0.5 equiv). After standing at r.t. for 16 h, Et3N·HCl was removed by filtration, the solvent was removed, and the crystalline product was recrystallized from benzene. Yield: 19.0%; mp 161.5-163 °C; [α]D 20 +290.1 (c 2.44, CH3CN). IR: 685, 1210, 1570, 1590, 3275 cm-1. 1H NMR [400 MHz, (CD3)2CO]: δ = 1.54 (d, J = 7.0 Hz, 3 H), 3.49 (dd, J = 13.3, 3.6 Hz, 1 H), 3.81 (dd, J = 13.3, 13.3 Hz, 1 H), 5.23 (dq, J = 7.0, 7.0 Hz, 1 H), 6.79-7.40 (m, 10 H), 8.28 (s, 1 H). 13C NMR [100.62 MHz, (CD3)2CO]: δ = 22.37 (CH3), 35.18 (d, CH2, J PC = 56.88 Hz, J HH = 144.27 Hz), 55.35 (CH), 167.61 (N=C), 151.74 (C i OP, d, J PC = 9.71 Hz), 144.24 (C i ), 122.34 (C o , J CH = 162.3 Hz), 125.23 (C o , J CH = 159.53 Hz), 129.23 (C m , J CH = 159.53 Hz), 129.89 (C m , J CH = 160.91 Hz), 126.87 (C p , J CH = 160.91 Hz), 127.96 (C p , J CH = 159.53 Hz). 31P NMR [(CD3)2CO, 162.98 MHz]: δ = 120.67. Anal. Calcd for C16H17N2OPS2: C, 55.14; H, 4.93; N, 8.04; P, 8.82; S, 18.41. Found: C, 55.47; H, 4.85; N, 8.02; P, 9.32; S, 18.23.
To 1 (2.0 g, 7.53 mmol, 1 equiv) in anhyd benzene (25 mL) at 0 °C was added a mixture of Et3N (0.53 g, 5.26 mmol, 0.7 equiv) and 3 (0.64 g, 5.26 mmol). Product 4b was isolated by the same procedure described above. Yield: 30.5%; mp 161.5-162 °C; [α]D 20 +289.3 (c 2.41, CH3CN). This product has similar spectral data.
The spectral data for 4a (from the mixture of diastereomers). 1H NMR [400 MHz, (CD3)2CO]: δ = 1.59 (d, J = 7.0 Hz, 3 H), 3.51 (dd, J = 13.3, 3.3 Hz, 1 H,), 3.89 (dd, J = 12.9, 2.9 Hz, 1 H), 5.35 (q, J = 7.0 Hz, 1 H), 7.12-7.43 (m, 10 H). 31C NMR [162.98 MHz, (CD3)2CO]: δ = 120.03.

7

( S C, R P )-2-(1-Phenyl)ethylamino-4-thioxo-4-phenoxy-1,3,4-thiazaphosphole ( 4d) Yield: 21.0%; mp 160-163 °C; [α]D 20 -277.4 (c 1.71, CH3CN). 1H NMR [400 MHz, (CD3)2CO]: δ = 1.53 (d, J = 8.0 Hz, 3 H), 3.50 (dd, J = 13.2, 3.9 Hz, 1 H), 3.80 (dd, J = 13.1, 13.1 Hz, 1 H), 5.23 (dq, J = 6.0, 6.0 Hz, 1 H), 6.8-7.30 (m, 10 H), 8.30 (s, 1 H). 13C NMR [100.62 MHz, (CD3)2CO]: δ = 21.93 (CH3), 34.34 (d, CH2, J PC = 56.16 Hz, J HH = 146.17 Hz), 54.73 (CH), 167.07 (N=C), 151.03 (C i OP, d, J PC = 9.63 Hz), 143.84 (C i ), 121.81 (C o , J CH = 162.22 Hz), 124.72 (C o , J CH = 159.01 Hz), 129.35 (C m , J CH = 159.01 Hz), 128.76 (C m , J CH = 160.62 Hz), 126.29 (C p , J CH = 154.2 Hz), 127.37 (C p , J CH = 159.01 Hz). 31P NMR [162.98 MHz, (CD3)2CO]: δ = 120.26.
The spectral data for 4c (from a mixture of diastereomers). 1H NMR [400 MHz, (CD3)2CO]: δ = 1.51 (d, J = 7.0 Hz, 3 H), 3.52 (dd, J = 13.3, 3.6 Hz, 1 H), 3.83 (dd, J = 13.3, 13.3 Hz, 1 H), 5.30 (q, J = 7.0 Hz, 1 H,), 7.14-7.39 (m, 10 H). 31P NMR [162.98 MHz, (CD3)2CO]: δ = 120.17.