PAPER
Synthesis of b-Phosphonato Unsaturated Thioimidates
2739
Diethyl 2-[(Benzoylimino)(methylsulfanyl)methyl]-3-
(dimethoxyphosphoryl)but-2-enedioate (3b)
Yield: 0.33 g (72%); yellow oil.
3JH,H = 7.2 Hz, 2 H, OCH2CH3), 4.16–4.25 [m, 4 H, PO(CH2CH3)2],
4.31 (q, 3JH,H = 7.2 Hz, 2 H, OCH2CH3), 7.44 (t, 3JH,H = 7.3 Hz, 2 H,
3
2 CH of Ar), 7.53 (t, JH,H = 7.4 Hz, 1 H, CH of Ar), 8.17 (d,
3JH,H = 7.0 Hz, 2 H, 2 CH of Ar).
IR (KBr): 1724 (C=O of ester), 1660 (PhC=O), 1611 (C=C), 1568
and 1443 (Ar), 1241 (P=O), 1176 and 1151 (C–O of ester), 1089
and 1021 cm–1 (P–OMe).
13C NMR (125.7 MHz, CDCl3): d = 13.40 (SCH2CH3), 13.69
3
(OCH2CH3), 13.85 (OCH2CH3), 15.99 [d, JP,C = 6.5 Hz,
PO(OCH2CH3)2], 26.58 (SCH2CH3), 62.19 (OCH2CH3), 62.65
3
1H NMR (500.1 MHz, CDCl3): d = 1.17 (t, JH,H = 7.4 Hz, 3
2
(OCH2CH3), 63.42 [d, JP,C = 4.7 Hz, PO(OCH2CH3)2], 128.22 (2
H,OCH2CH3), 1.32 (t, 3JH,H = 7.3 Hz, 3 H,OCH2CH3), 2.64 (s, 3 H,
CH of Ar), 130.45 (2 CH of Ar), 132.98 (CH of Ar), 134.23 (Cipso
of Ar), 135.28 (d, 1JP,C = 167.1 Hz, POC=C), 144.30 (d, 2JP,C = 6.2
3
SCH3), 3.65 [d, JP,H = 11.5 Hz, 6 H, PO(OCH3)2], 4.21 (q,
3
3JH,H = 7.0 Hz, 2 H, OCH2CH3), 4.31 (q, JH,H = 7.1 Hz, 2 H,
3
Hz, POC=C), 162.31 (d, JP,C = 24.0 Hz, C=NCO), 164.71 (d,
3
OCH2CH3), 7.43 (t, JH,H = 7.1 Hz, 2 H, 2 CH of Ar), 7.53 (t,
3
2JP,C = 9.5 Hz, CO2Et), 171.62 (d, JP,C = 7.2 Hz, CO2Et), 175.91
(PhC=O).
3JH,H = 7.1 Hz, 1 H, CH of Ar), 8.15 (d, 3JH,H = 7.9 Hz, 2 H, 2 CH of
Ar).
31P NMR (202.4 MHz, CDCl3): d = 5.67.
13C NMR (125.7 MHz, CDCl3): d = 13.67 (OCH2CH3), 13.81
2
(OCH2CH3), 15.21 (SCH3), 53.63 [d, JP,C = 5.3 Hz, PO(OCH3)2],
MS: m/z (%) = 448 (8), 410 (21), 384 (31), 334 (41), 277 (17), 192
(45), 105 (100), 77 (79), 43 (55).
62.38 (OCH2CH3), 62.81 (OCH2CH3), 128.35 (2 CH of Ar), 130.36
(2 CH of Ar), 133.10 (CH of Ar), 134.05 (Cipso of Ar), 134.69 (d,
Anal. Calcd for C22H30NO8PS (499.51): C, 52.90; H, 6.05; N, 2.80.
Found: C, 52.95; H, 6.08; N, 2.79.
2
1JP,C = 169.0 Hz, POC=C), 144.14 (d, JP,C = 6.3 Hz, POC=C),
3
2
161.40 (d, JP,C = 24.2 Hz, C=NCO), 164.31 (d, JP,C = 9.6 Hz,
CO2Et), 171.50 (d, 3JP,C = 7.1 Hz, CO2Et), 175.87 (PhC=O).
31P NMR (202.4 MHz, CDCl3): d = 8.61.
References
MS: m/z (%) = 457 (7, [M+]), 410 (21), 384 (19), 339 (27), 279 (58),
105 (100), 77 (42), 51 (12).
(1) (a) Neilson, D. G. In The Chemistry of Amidines and
Imidates; Patai, S., Ed.; Wiley: London, 1975, 385–489.
(b) Yokoyama, M.; Menjo, Y.; Wei, H.; Togo, H. Bull.
Chem. Soc. Jpn. 1995, 68, 2735. (c) Lerestif, J. M.;
Bazureau, J. P.; Hamelin, J. Tetrahedron Lett. 1993, 34,
4639. (d) Doise, M.; Blondeau, D.; Sliwa, H. Synth.
Commun. 1992, 22, 2891. (e) Neunhoeffer, H.; Karafiat, U.;
Kohler, G.; Sowa, B. Liebigs Ann. Chem. 1992, 115.
(f) Alanine, A. I. D.; Fishwick, C. W. G. Tetrahedron Lett.
1989, 30, 4443.
Anal. Calcd for C19H24NO8PS (457.43): C, 49.89; H, 5.29; N, 3.06.
Found: C, 49.92; H, 5.27; N, 3.08.
Dimethyl 2-[(Benzoylimino)(ethylsulfanyl)methyl]-3-(diethoxy-
phosphoryl)but-2-enedioate (3c)
Yield: 0.35 g (75%); yellow oil.
IR (KBr): 1729 (C=O of ester), 1657 (PhC=O), 1612 (C=C), 1565
and 1430 (Ar), 1250 (P=O), 1178 and 1155 (C–O of ester), 1041
and 1013 cm–1 (P–OEt).
(2) Roger, R.; Neilson, D. G. Chem. Rev. 1961, 61, 179.
(3) Takahata, H.; Takamatsu, T.; Yamazaki, T. J. Org. Chem.
1989, 54, 4812.
3
1H NMR (500.1 MHz, CDCl3): d = 1.17 [t, JH,H = 7.0 Hz, 6 H,
PO(OCH2CH3)2], 1.47 (t, 3JH,H = 7.4 Hz, 3 H, SCH2CH3), 3.29 (q,
3JH,H = 7.4 Hz, 2 H, SCH2CH3), 3.72 (s, 3 H, OCH3), 3.87 (s, 3 H,
OCH3), 3.95–4.02 [m, 4 H, PO(CH2CH3)2], 7.44 (t, 3JH,H = 7.7 Hz,
2 H, 2 CH of Ar), 7.52 (t, 3JH,H = 7.4 Hz, 1 H, CH of Ar), 8.17 (d,
3JH,H = 7.1 Hz, 2 H, 2 CH of Ar).
(4) Hashimoto, M.; Matsumoto, M.; Terashima, S. Tetrahedron
2003, 59, 3041.
(5) (a) Chang, R. K.; Dipardo, R. M.; Kuduk, S. D. Tetrahedron
Lett. 2005, 46, 8513. (b) Kuduk, S. D.; Ng, C.; Chang, R. K.;
Bock, M. G. Tetrahedron Lett. 2003, 44, 1437.
(6) (a) Gutschow, M.; Powers, J. C. J. Org. Chem. 2001, 66,
4723. (b) Dufour1, E.; Tam, W.; Naëgler, D. K.; Storer, A.
C.; Meènard, R. FEBS Lett. 1998, 433, 78.
(7) Sawada, J.; Okamoto, K.; Yamamotoa, T.; Kanbarab, T.
Tetrahedron Lett. 2007, 48, 8603.
(8) Parlato, M. C.; Kamat, M. N.; Wang, H.; Stine, K. J.;
Demchenko, A. V. J. Org. Chem. 2008, 73, 1716.
(9) (a) Kantlehner, W.; Mergen, W. W. In Comprehensive
Organic Functional Group Transformations, Vol. 5;
Katritzky, A. R.; Meth-Cohn, O.; Rees, C. W., Eds.;
Elsevier: Oxford, 1995, 653–724. (b) Bonnet, R. In The
Chemistry of the Carbon–Nitrogen Double Bond; Patai, S.,
Ed.; Wiley-Interscience: New York, 1970, 597–662.
(10) Dosio, F.; Arpicco, S.; Brusa, P.; Stella, B.; Cattel, L.
J. Controlled Release 2001, 76, 107.
13C NMR (125.7 MHz, CDCl3): d = 13.29 (SCH2CH3), 15.90 [d,
3JP,C = 6.6 Hz, PO(OCH2CH3)2], 26.66 (SCH2CH3), 53.06 (OCH3),
53.35 (OCH3), 63.53 [d, 2JP,C = 4.9 Hz, PO(OCH2CH3)2], 128.25 (2
CH of Ar), 130.50 (2 CH of Ar), 133.07 (CH of Ar), 134.16 (Cipso
of Ar), 135.37 (d, 1JP,C = 167.5 Hz, POC=C), 143.52 (d, 2JP,C = 6.3
Hz, POC=C), 162.19 (d, JP,C = 24.1 Hz, C=NCO), 165.08 (d,
2JP,C = 9.2 Hz, CO2Me), 171.89 (d, 3JP,C = 7.1 Hz, CO2Me), 175.98
(PhC=O).
3
31P NMR (202.4 MHz, CDCl3): d = 5.34.
MS: m/z (%) = 442 (12), 410 (35), 334 (23), 306 (17), 262 (33), 105
(100), 77 (65), 51 (15).
Anal. Calcd for C20H26NO8PS (471.46): C, 50.95; H, 5.56; N, 2.97.
Found: C, 50.99; H, 5.57; N, 2.98.
(11) (a) Challis, B. C.; Challis, J. A. In The Chemistry of Amides;
Zabicky, J., Ed.; Wiley-Interscience: New York, 1970, 731–
857. (b) Walter, W.; Voss, J. In The Chemistry of Amides;
Zabicky, J., Ed.; Wiley: New York, 1970, 383–475.
(c) Challenger, S. In Comprehensive Organic Functional
Group Transformations, Vol. 5; Katritzky, A. R.; Meth-
Cohn, O.; Rees, C. W., Eds.; Elsevier: Oxford, 1995, 725–
740. (d) Pearson, W. H.; Stevens, E. P. J. Org. Chem. 1998,
63, 9812. (e) Wrona, A.; Palusiak, M.; Zakrzewski, J. J.
Organomet. Chem. 2008, 693, 263.
Diethyl 2-[(Benzoylimino)(ethylsulfanyl)methyl]-3-(diethoxy-
phosphoryl)but-2-enedioate (3d)
Yield: 0.35 g (70%); yellow oil.
IR (KBr): 1725 (C=O of ester), 1655 (PhC=O), 1616 (C=C), 1565
and 1459 (Ar), 1244 (P=O), 1170 and 1161 (C–O of ester), 1090
and 1014 cm–1 (P–OEt).
3
1H NMR (500.1 MHz, CDCl3): d = 1.18 (t, JH,H = 7.0 Hz, 3 H,
3
OCH2CH3), 1.22 (t, JH,H = 7.1 Hz, 3 H, OCH2CH3), 1.32 [t,
3
3JH,H = 7.1 Hz, 3 H, PO(OCH2CH3)2], 1.46 (t, JH,H = 7.3 Hz, 3 H,
3
SCH2CH3), 3.28 (q, JH,H = 7.3 Hz, 2 H, SCH2CH3), 3.98 (q,
Synthesis 2009, No. 16, 2737–2740 © Thieme Stuttgart · New York