ChemInform Abstract: DARSTELLUNG UND UNTERSUCHUNG VON BETA‐KETO‐SYMM.‐TRIAZINEN

Abstract

Cyanurchlorid (I) reagiert mit den Enaminen (II) bei nachfolgender Hydrolyse zu den Titelverbindungen (III).

Synthesis and tautomerism study of 6-benzoylmethyl-1,3,5-triazin-2,4-diamine

“…However, these factors have not been systematically studied for acylmethyl-1,3,5-triazines and some questionable arbitrarily chosen assignments have been appearing [6,7]. In some reported cases, the potential existence of enaminone form C was ignored [8,9] even though this form appeared to be predominant in other studies [10,11] and was the only one found in the solid state by X-ray crystallography [12].…”

Thermal rearrangement of .alpha.-oxo-.alpha.,.beta.-unsaturated azines to N-substituted pyrazoles

“…Additional support was provided by the conversion of pure llx to a mixture (as determined by thin-layer chromatography) of llx and 12x upon heating at 170 °C for 2 h. Presumably stabilization of the enol form in these cases is provided by intramolecular hydrogen bonding with N-2 of the pyrazole ring as in 27. Similar enol stabilization is seen in -triazinyl ketones (e.g., 28), 9 We can offer no ex-27 planation as to why these two systems were the only ones in which the enol was isolable.…”

“…We have extended this sequence to include the reactions of 22 with a variety of other ,/3-unsaturated aldehydes and ketones (26b-p), summarized in Table I. Azines (9) were isolable in approximately half of the reactions, pyrazoles, 11, and/or 12, being formed directly in the remainder. The a-oxo-a,|S-unsaturated azines, ranging in color from yellow to orange, could be converted to the colorless pyrazoles 11/12 in good yield by thermolysis (Table II).…”

“…Table IV. LH NMR Parameters for Azines (9) and Pyrazoles (11/12)°9 h 2.22 (s, 3 H, C(3)-CH3), 6.62 ("d", J s 6 Hz, 2 H, C(4)-H + C(5)-H), 7.03 (s, 4 H, CgHiCl), 7.2 (m, 6 H, aromatic), 7.70 (m, 4 H, aromatic ortho to C=0/C=N) 9i 2.01 (s, 3 H, C(2)-CH3), 2.39 (s, 3 H, C(1)-CH3), 6.90 ("d", J 3= 5 Hz, 2 H, C(4)-H + C(5)-H), 7.25 (m, 5 H, aromatic), 7.85 ("t", Ja 4 Hz, 1 H, C(3)-H) 9j 6.73 (d, J a 8.0 Hz, 2 H, C(4)-H + C(5)-H), 6.93-7.46 (m, 11 H, aromatic), 7.75 (m, 4 H, aromatic ortho to C=0/C=N), 8.20 (dd, J = 8.0,1.5 Hz, 1 H, C(3)-H) 9k 6.29-6.38 (m, 2 H, furan C(3)-H + C(4)-H), 6.63-6.75 (m, 2 H, C(4)-H + C(5)-H), 7.25-7.48 (m, 7 H, aromatic + furan C(5)-H), 7.72-7.98 (m, 4 H, aromatic ortho to C=0/C=N), 8.36 (dd, J = 6.0, 3.3 Hz, 1 H, C(3)-H) 9r 7.35-7.60 (m, 12 H, aromatic + C(5)-H), 7.75-8.07 (m, 4 H, aromatic ortho to C=0/C=N), 8.28 (s, 1 H, C(3)-H) 9s 1.44 (br m, 4 H, -CH2CH2CH2CH2-), 1.95 (br m, 4 H, -CH2CH2CH2CH2-), 6.12 (m, 1 H, C(5)-H), 7.3 (m, 6 H, C(3)-H) 9u 2.16 (m, 2 H, -CH2CH20-), 3.06 (br t, J a 6 Hz, 2 H, -CH2CH20), 3.85 (br s, 2 H, C=CCH20-), 6.28 (m, 1 H, C(5)-H), 7.2 (m, 6 H, aromatic), 7.7 (m, 4 H, aromatic ortho to C=0/C-N), 7.85 (s, 1 H, C(3)-H) 9v 1.66 (br q, J a 7 Hz, 2 H, -CH2CH2CH2-), 2.12 (m, 4 H, -CH2CH2CH2-), 6.12 (m, 1 H, C(5)-H), 7.22 (m, 6 H, aromatic), 7.68 (m, 4 H, aromatic ortho to C=0/C=N), 8.22 (s, 1 H, C(3)-H) 9x 1.73 (m, 2 H, -CH2CH2CH2-), 2.67 (m, 4 H, -CH2CH2CH2-),…”

The structure of 2,4,6-tris[di(tert-butoxycarbonyl)methylidene]-hexahydro-1,3,5-triazine

“…In the presence of keto or aldehyde groups in the side chain (β oxoalkyl azines), keto-enol tautomerism occurs along with the azinyl-ylidene tautomerism (Scheme 1). 1, 3 The energy range corresponding to a comparable tautomer contents is 0-5 kcal mol -1 ; according to spectroscopy, only one tautomer exists in many cases, which means that tautom erism is practically missing. 1 In the 1,3,5 triazine series, compounds containing one di(alkoxycarbonyl)methyl group are believed to be aro matic.…”