1610
M. S. Yusubov et al. / Tetrahedron 58 42002) 1607±1610
J9 Hz, phenyl-H4), 7.94 Ed, 2?, J9 Hz, phenyl-H2 and
H6), 8.12 Ebr.s, 1H, pyrazole-H3), 8.57 Ebr.s, 1H, pyrazole-
H5). Anal. Calcd for C11H8N2O2: C, 65.99; H, 4.03; N,
13.99. Found: C, 65.9; H, 4.0; N, 14.0.
3.1.11. 1-Biphenyl-4-yl-2-)6,7,9,10,12,13,15,16-octahydro-
5,8,11,14,17-pentaoxa-benzocyclopentadecen-2-yl)-ethane-
1,2-dione )8b). Yield 84%. Colorless powder with mp 123±
1248C Ebenzene); 1H NMR EDMSO-d6) d 3.57±3.67 Em, 8H,
ECH2CH2)2), 3.74±3.83 Em, 4H, ECH2CH2O)2Ar), 4.11±4.20
Em, 4 H, ECH2O)2Ar), 7.12 Ed, J9 Hz, 1H), 7.37±7.66 Em,
3.1.6. 1-)4-Nitrophenyl)-2-)1H-pyrazol-4-yl)-ethan-1,2-
dione )3d). A mixture of 4-E4-nitrophenylethynyl)pyrazole
E2d) E337 mg, 1.58 mmol) and palladiumEII) chloride
E30 mg, 0.17 mmol) in DMSO E8 ml) was stirred at 135±
1408C for 7 h. Workup as for the foregoing 1,2-diketone 3c
gave dione 3d E283 mg, 73%) as yellow needles, mp 150±
1518C Eethanol); IR: nmax1493, 1533, 1603, 1650, 1671,
3116 cm21; 1H NMR ECDCl3) d 3.30 Ebr.s, 2?, pyrazole-H3
and H5), 8.28 Ed, 2H, J9 Hz, phenyl-H2 and H6), 8.46 Ed,
0
0
5H), 7.72±7.84 Em, 20H), 7.91 Ed, J9 Hz, 2H, H3 , H5 ), 7.97
0
Ed, J9 Hz, 2H, H2 , H6 ). Anal. Calcd for C28H28O7: C,
70.57; H, 5.92. Found: C, 70.5; H, 5.8.
Acknowledgements
We thank Dr S. V. Klyatskaya for supplying samples of
2-E4-methoxy-phenylethynyl)- and 2-biphenyl-4-ylethynyl-
6,7,9,10,12,13,15,16-octahydro-5,8,11,14,17-pentaoxa-benzo-
cyclopentadecene. This work was ®nancially supported by
the Russian Foundation for Basic Research EProject No.
00-03-32812a) and Grant CRDF REC-008.
1
2H, J9 Hz, phenyl-H3 and H5); H NMR EDMSO-d6) d
7.39 Ebr.s, 2?, pyrazole-H3 and H5), 8.13 Ed, 2H, J9 Hz,
phenyl-H2 and H6), 8.37 Ed, 2H, J9 Hz, phenyl-H3 and H5).
Anal. Calcd for C11H7N3O4: C, 53.88; H, 2.88; N, 17.14.
Found: C, 53.7; H, 2.8; N, 17.1.
Alkynes 2a, 2b, 2e, 7a and 7b were oxidized in exactly the
same manner as 2c. Alkynes 2f and 6 were not oxidized
under the foregoing conditions while oxidation of alkynes
5a, 5b and 9 gave a complex mixture of products.
References
1. Mazik, M.; Boese, R.; Sustmann, R. Tetrahedron 1996, 52,
3939.
2. El-Samii, Z. K. A.; El-Feky, S. A.; Jaeda, M. I.; Moustafa,
M. A. A. Pol. J. Chem. 1995, 69, 61.
3.1.7. 1-Phenyl-2-)1,3,5-trimethyl-1H-pyrazol-4-yl)-ethan-
1,2-dione )3a). Yield 82%. Yellowish oil; 1H NMR ECD2Cl2)
d 2.16 Es, 3H, pyrazole-3-CH3), 2.42 Es, 3H, pyrazole-5-
CH3), 3.72 Es, 3H, N±CH3), 7.51 Et, 2H, J 9 Hz, phenyl-
H3 and H5), 7.69 Et, 1H, J9 Hz, phenyl-H4), 7.51 Ed, 2H,
J9 Hz, phenyl-H2 and H6). Anal. Calcd for C14H14N2O2: C,
69.41; H, 5.82; N, 11.56. Found C, 69.3; H, 5.9; N, 11.4.
3. Mitchel, R. H.; Iyer, V. S. Tetrahedron Lett. 1993, 34, 3683
and references therein.
4. Prasad, K. R. K.; Joshi, N. N. J. Org. Chem. 1996, 61, 3888
and references therein.
5. Bergman, J.; Janosik, T.; Johnson, A.-L. Synthesis 1999, 580.
6. Filimonov, V. D.; Yusubov, M. S.; Ki-Whan, C. Uspekhi
Khim. 1998, 803.
3.1.8. 1-)1,5-Dimethyl-1H-pyrazol-4-yl)-2-phenylethan-
1,2-dione )3b). Yield 74%. Yellowish powder with mp
89±89.58C Ebenzene±hexane); IR: nmax1459, 1489,
7. Yusubov, M. S.; Filimonov, V. D.; Vasilyeva, V. P.; Ki-Whan,
C. Synthesis 1995, 1234.
8. Yusubov, M. S.; Ki-Whan, C.; Krasnokutskaya, E. A.; Vasil'eva,
V. P.; Filimonov, V. D. Zh. Org. Khim. 1995, 31, 1675.
9. Stephens, R. D.; Castro, C. E. J. Org. Chem. 1963, 28, 3313.
10. Cassar, L. J. Organomet. Chem. 1975, 93, 253.
11. Dieck, H. A.; Heck, F. P. J. Organomet. Chem. 1975, 93, 259.
12. Sonogashira, K.; Tohda, Y.; Hagihara, N. A. Tetrahedron Lett.
1975, 50, 4467.
1542, 1597, 1654, 1672, 3061, 3130 cm21 1H NMR
;
EDMSO-d6) d 2.23 Es, 3H, 5-CH3), 3.87 Es, 3H, N±CH3),
7.58 Et, 2H, J9 Hz, H3, H5), 7.72 Et, 1H, J9 Hz, H4), 7.89
Ed, 2H, J9 Hz, H2, H6), 8.32 Es, 1H, pyrazole-H5). Anal.
Calcd for C13H12N2O2: C, 68.41; H, 5.30; N, 12.27. Found:
C, 68.5; H, 5.4; N, 12.1.
13. Tretyakov, E. V.; Knight, D. W.; Vasilevsky, S. F. J. Chem.
Soc., Perkin Trans. 1 1999, 3713.
3.1.9. 1-)3-Amino-1-methyl-1H-pyrazol-4-yl)-2-)4-meth-
oxyphenyl)-ethan-1,2-dione )3e). Yield 42%. Yellow
powder with mp 172±1738C Ebenzene); IR: nmax1513,
1574, 1602, 1652, 2846, 2938, 3013, 3194, 3281,
14. Tretyakov, E. V.; Elguero, J.; Vasilevsky, S. F., manuscript in
preparation.
15. Prikhod'ko, T. A.; Vasilevsky, S. F. Izv. Akad. Nauk, Ser.
Khim. 2001, 7, 1012±1014.
1
3437 cm21; H NMR EDMSO-d6) d 3.64 Es, 3H, N±CH3),
3.88 Es, 3H, O±CH3), 6.00 Ebr. s, 2H, NH2), 7.13 Ed, 2H,
J9 Hz, H3, H5), 7.90 Ed, 2H, J9 Hz, H2, H6), 7.97 Es, 1H,
pyrazole-H5). Anal. Calcd for C13H13N3O3: C, 60.22; H,
5.05; N, 16.21. Found: C, 60.4; H, 5.3; N, 16.1.
16. Klyatskaya, S. V.; Tretyakov, E. V.; Vasilevsky, S. F. Izv.
Akad. Nauk, Ser. Khim. 2001 in press.
17. Brandsma, L.; Vasilevsky, S. F.; Verkruijsse, H. D. Appli-
cation ofTransition Metal Catalysts in Organic Synthesis ;
Springer: Heidelberg, 1998.
3.1.10.
1-)4-Methoxy-phenyl)-2-)6,7,9,10,12,13,15,16-
18. Vasilevsky, S. F.; Shvartsberg, M. S. Izv. Akad. Nauk, Ser.
Khim. 1980, 1071.
octahydro-5,8,11,14,17-pentaoxa-benzocyclopentadecen-
2-yl)-ethane-1,2-dione )8a). Yield 79%. Colorless powder,
mp 104±104.58C Ebenzene); IR: nmax1424, 1461, 1511,
19. Giles, D.; Parnell, E. W.; Rerwick, J. D. J. Chem. Soc. 4C)
1966, 1179.
È
20. HuÈttell, R.; Schafer, O.; Jochum, P. Liebigs Ann. Chem. 1955,
593, 200.
1572, 1598, 1662 cm21 1H NMR EDMSO-d6) d 3.57±
;
3.67 Em, 12H), 3.74±3.83 Em, 4H, ECH2CH2O)2Ar), 3.87
Es, 3H, CH3), 4.08±4.20 Em, 4H, ECH2O)2Ar), 7.04±7.19
21. Austin, W.; Bilow, N.; Kelleghan, W. J.; Lau, K. S. Y. J. Org.
Chem. 1981, 46, 2280.
0
0
Em, 3H, H2 , H6 , H20), 7.34 Ed, 1H, J9 Hz, H19), 7.51 Es,
0
0
1H, H3), 7.86 Ed, J9 Hz, 2H, H3 , H5 ). Anal. Calcd for
C23H26O8: C, 64.18; H, 6.09. Found: C, 64.4; H, 6.1.