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7551
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column chromatography (CHCl3–MeOH, 2:1) to afford pyrazolone
53. Yield: 0.32 g (75%); yellow viscous oil; (Found: C, 27.19; H, 3.42;
Br, 26.59. C10H5BrF4N2 requires: C, 27.47; H, 3.62; Br, 26.11%.) 1H
NMR (200 MHz, MeOH-d4):
d
¼1.59–1.74 (m, 2H, CH2CH2N), 1.86–
2.09 (m, 2H, Het-CH2), 2.96 (t, 3JH,H¼7.6 Hz, 2H, CH2N), 5.0 (br s, 5H,
OH, NH, NH3); 13C NMR (50.3 MHz, MeOH-d4): 21.1 (Het-CH2), 32.8
1
(CH2CH2N), 40.6 (CH2N), 77.1 (4-C), 120.6 (q, JC,F¼271.7 Hz, CF3),
150.9 (q, 2JC,F¼36.3 Hz, 5-C), 177.9 (3-C); 19F NMR (188 MHz, MeOH-
d4):
d
¼ꢁ67.28 (s, CF3); MS [ESI, MeOH, positive]: m/z (%)¼226 (100)
[Qþ], 209 (10) [QꢁNH3]þ; MS [ESI, MeOH, negative]: m/z (%)¼691
(100) [2Qþ3Br]ꢁ, 386 (100) [Qþ2Br]ꢁ.
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Acknowledgements
We are grateful to Dr. M. Braun, Solvay Organics GmbH, Bensberg,
Germany, forthegenerousgiftofchemicals. Mrs. D.KemkenandDr. T.
Du¨lcks, Institute of Organic Chemistry, University of Bremen, Ger-
many, are thanked for recording mass spectra, and Mr. P. Brackmann,
Institute of Inorganic & Physical Chemistry, University of Bremen,
Germany, is thanked for the X-ray diffraction measurements.
24. Neyland, O. Y.; Stradyn’, Ya. P.; Silin’sh, E. A.; Balode, D. R.; Valtere, S. P.; Kadysh,
V. P.; Kalnin’, S. V.; Kampar, V. E.; Mazheyka, I. B.; Taure, L. F. Stroenie i Tauto-
mernye Prevrashcheniya
Riga, 1977.
b-Dikarbonil’nykh Soedineniy (in Russian); Zinatne:
Supplementary data
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Supplementary data associated with this article can be found in
26. The 1,3-dicarbonyl compounds are depicted as their major U-enol tauto-
mer24,25,27 through this paper.
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from air: 100 mg of the pale yellow needles of its diketo form became red after
maintaining under air for 48 h (the resulting solid has mp 115–119 ꢀC). Ac-
cording to 19F NMR (anhyd THF) spectrum, it is almost pure hydrate of 8a.
Noteworthy, thiochromones 8b,c appeared to be much less hygroscopic
comparing to CF3-analogue 8a: although 100 mg of 8c (pale yellow crystals)
did not changed optically if maintained under air for 72 h, a significant
amount (ca. 29%) of 8c$H2O could be detected by 19F NMR (see experimental
part for dF). 100 mg of 8b (pale yellow needles) did not changed optically if
maintained under air for 72 h. Only minimal amount (ꢃ3%) of 8b$H2O could
2
be detected by 19F NMR (188 MHz, CDCl3):
d
¼ꢁ136.79 (dt, JF,H¼52.3 Hz,
3JF,F¼7.8 Hz, 2F, CF2H), ꢁ131.11 (td, JF,F¼7.8 Hz, 3JF,Hz6 Hz, 2F, COCF2). It
should be noted, that the similar tendency to form hydrates (i.e., gem-diols
across the polyfluoroacyl moiety) was observed for the related chromones35a
and coumarins.35b
3
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in preparation.
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submitted for publication.
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