386 Li et al.
1
for 2 h. The reaction mixture was evaporated in
vacuo and then purified by chromatography on a sil-
ica. Elution with ethyl acetate and petroleum ether
(60–90◦C) gave 10 as a yellow liquid (0.41 g, 53.3%
(1.6 g, 50.0% yield). H NMR (CDCl3) δ 2.60 (s, 6H,
SCH3), 7.40–8.20 (m, 5H, C6H5). (Ref. [7]: 43.0%,
white solid, m.p. 46–47◦C). At the same time, three
by-products were also afforded: PhCO NH CS2Me
yield, 0.5%; m.p. 133–134◦C; 1H NMR (CDCl3) δ 2.40
(s, 3H, SCH3), 9.24 (s, 1H, N H), 7.20–8.0 (m, 5H,
C6H5); PhCO NMe CS2Me yield, 10.4%; m.p. 68–
69◦C; 1H NMR (CDCl3) δ 2.60 (s, 3H, SCH3), 3.70 (s,
3H, NCH3), 7.20–7.80 (m, 5H, C6H5 ); PhCO NMe2
1
yield). H NMR(CDCl3) δ 1.17 (m, 6H, OCH2CH3),
2.66 (s, 3H, SCH3), 4.01 (m, 4H, OCH2CH3), 5.73 (d,
2 JPH = 23 Hz, 1H, PCH), 7.36 (m, 10H, C6H5 ). Anal.
Calcd for C20H24N3OO3PS: C, 57.43; H, 5.86; N, 10.18;
Found: C, 57.54; H, 5.79; N, 10.07.
1
yield, 35.8%; yellow oil; H NMR (CDCl3) δ 3.00 (s,
6H, N(CH3)2), 7.40 (s, 5H, C6H5 ).
REFERENCES
6: A solution of malononitrile (11.3 g, 0.172 mol),
triethyl orthoformate (37 g, 0.25 mol), and acetic an-
hydride (41.7 g, 0.4 mol) was heated to 100◦C for
4 h. The resulting mixture was distilled to afford the
fractions: 110–114◦C/0.9 mmHg, 16.5 g, yield: 78.6%;
m.p. 65–67◦C. (Ref. [5]: m.p. 67–68◦C).
[1] (a) Takematsu, T.; Konnai, M.; Tachibana, K.;
Tsuruoka, T.; Inouye, S.; Watanabe, T. US Patent 4 265
654, 1981; (b) Schuster, G. Ger (East) DD 1991, 284,
155; (c) Ling, Y. X.; Zhang, K. S.; Qiu, D. W. Chem
J Chinese Universities 1996, 17(8), 1247; (d) Borloo,
M.; Jiao, X. Y.; Wojtowicz, H.; Rajan, R.; Verbruggen,
C.; Augustyus, K.; Hacmers, A. Synthesis 1995, 1074;
(e) Dai, Q.; Chen, R. Y. Heteroatom Chem 1997, 8(3),
203; (f) Wang, Q. M.; Li, Z. G.; Huang, R. Q.; Cheng,
J. R. Heteroatom Chem 2001, 12(2), 68; (g) Wang, Q.
M.; Chen, Z.; Zeng, Q.; Huang, R. Q. Heteroatom Chem
1999, 10(3), 209.
[2] (a) Kitazaki, T.; Tamura, N.; Tasaka, A.; Matsushita, Y.;
Hayashi, R.; Obouogi, K.; Itoh, K. Chem Pharm Bull
1996, 44(2), 314–327; (b) Hutchinson, D. K. WO Patent
23, 788, 1996; (c) Morimoto, K.; Ogura, T.; Nagaoka, T.
WO Patent 24, 589, 1996; (d) Chamberlain, K. Pestic
Sci 1991, 31, 185; (e) Pirre, C. J. EP 258160, 1988.
[3] (a) Yuan, C. Y.; Li, C. Z. Synthesis 1996, 507; (b) Yuan,
C. Y. Phosphorus Sulfur Silicon 1995, 106, 115; (c) Diel,
P.; Maier, L. Phosphorus Sulfur Silicon 1988, 36, 85;
(d) Rachon, J.; Wasielewski, C. Rocz Chem 1976, 50,
477.
[4] Texier-Boullet, F.; Foucaud, A. Tetrahedron Lett 1983,
21, 4847.
[5] Jones, R. G. J Am Chem Soc 1952, 74, 4889.
[6] Wang, X. J.; Huang, Z. T. Acta Chim Sinica 1989, 47,
890.
[7] Sato, M.; Fukada, N.; Kurauchi, M.; Takeshima, T.
Synthesis 1981, 7, 554.
[8] (a) Li, Z. G.; Huang, R. Q.; Yang, Z.; Li, H. Y. Chem
J Chin Universities 1998, 19(12), 1970; (b) Li, Z. G.;
Huang, R. Q.; Shao, R. L.; Yang, Z.; Long, Y. X. Phos-
phorus Sulfur Silicon 1999, 155, 137.
9: A mixture of 6 (2.36 g, 19.4 mmol), 3 (5.0 g,
19.4 mmol), and ethanol (30 ml) was heated under
reflux for 5 h. The reaction mixture was cooled down
to room temperature, concentrated in vacuo, and the
residue was dissolved in CH2Cl2 (40 ml), which was
washed with 5% sodium carbonate solution and wa-
ter, dried with anhydrous Na2SO4, and concentrated
in vacuo to give the crude product as viscous liquid.
The addition of ether gave white solid (5.2 g, 68.4%
yield). m.p. 117–118.5◦C. IR (KBr) ν/cm−1 3185.0
(N H), 2208.0 (C N), 1662.7 (N H), 1233.2 (P O),
1020.1(P O C). 1H NMR (CDCl3) δ 1.21 (m, 6H,
OCH2CH3), 4.07 (m, 4H, OCH2CH3), 5.33 (br, 2H,
2
NH2), 5.74 (d, JPH = 24 Hz, 1H, PCH), 7.33–7.50
(m, 6H, Harom). Anal. Calcd for C15H19N4O3P: C,
53.89; H, 5.73; N, 16.76; Found: C, 53.49; H, 5.65; N,
16.75; MS (EI, 15 ev) m/z 334 (M, 13%), 197 (C11H9N4,
100%), 91 (C7H7, 48%).
8: The compound was synthesized from the reac-
tion of 5 and 3 as described for 9. White crystal. Yield,
1
50.4%. m.p. 128.5–130◦C. H NMR (CDCl3) δ 1.19
(m, 6H, OCH2CH3), 3.99 (m, 4H, OCH2CH3), 4.20
2
(s, 2H, SCH2), 5.50 (br, 2H, NH2), 5,76 (d, JPH = 23
Hz, 1H, PCH), 7.17–7.50 (m, 10H, Harom). Anal.
Calcd for C22H25N4O3PS: C, 57.88; H, 5.52; N, 12.27;
Found: C, 57,98; H, 5.44; N, 12.05.
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Magnetic Resonance Spectra 16549M; (b) Kristian, P.;
Kutschy, P.; Dzurilla, M. Coll Czech Chem Commun
1979, 44, 1324; (c) Ueno, Y.; Nakai, T.; Okawara, M.
Bull Chem Soc Jpn 1971, 44, 841.
10: A solution of 3 (0.46 g, 1.8 mmol) and 4
(0.41 g, 1.8 mmol) in ethanol (20 ml) was refluxed