Reactions of azines with electron-deficient alkynes. Formation of 1,5-dihydropyrazolo[1,2-a]pyrazoles, .alpha.,.beta.-unsaturated azines, and N-allyl- and N-propenylpyrazoles

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

“…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-),…”

“…6.87 (t, J = 2.5 Hz, 1 H, C(5)-H), 7.1 (m, 11 H, aromatic), 7.7 (m, 4 H, aromatic ortho to C=0/C=N) lit 1.76 (m, 2 H, -CH2CH2CH20-), 2.44 (br t, J a 6 Hz, 2 H, -CH2CH2CH20-), 4.06 (br t, J a 5 Hz, 2 H, -CH2CH2CH20-), 5.96 (br s, 1 , -OH), 7.2 (m, 10 H, aromatic), 8.01 (s, 1 H, C(3)-H) 11x1.96 (br, p,bJ a 7 Hz, 2 H, -CH2CH2CH2-), 2.95 (br q, J a 7 Hz, 4 H, -CH2CH2CH2-), 6.36 (s, 1 H, -OH), 6.9-7.S (m, 15 H, aromatic) 12c 1.20 (t, J = 6.0 Hz, 3 H, CH3CH20-), 4.20 (q, J = 6.0 Hz, 2 H, CH3CH20-), 4.80 (s, 2 H, C(2)-H2), 6.50 (s, 1 H, C(4)-H), 7.1-7.5 (m, 12 H, aromatic + vinyl) 12d 1.20 (t, J = 6.0 Hz, 3 H, CH3CH20-), 4.17 (q, J = 6.0 Hz, 2 H, CH3CH20-), 4.80 (s, 2 H, C(2)-H2), 6.46 (s, 1 H, C(4)-H), 7.02-7.50 (m, 10 H, aromatic + vinyl) 12e 1.20 (t, J = 6.7 Hz, 3 H, CH3CH20-), 4.12 (q, J = 6.7 Hz, 2 H, CH3CH20-). 4.68 (s, 2 H, C(2)-H2), 5.28 (d, JPH = 14.6 Hz, 2 H, -CH2P+Ph3Br-), 6.39 (d, JPH = 1.3 Hz, 1 H, C(4)-H), 7.08-8.10 (m, 20 H, aromatic) 12f 1.20 (t, J = 7.3 Hz, 3 H, CH3CH20-), 4.16 (q, J = 7.3 Hz, 2 H, CH3CH20-), 4.70 (s, 2 H, C(2)-H2), 5.34 (d, JPH = 14.0 Hz, 2 H, -CH2P+Ph3Br-), 6.39 (d, JPH = 1.3 Hz, 1 H, C(4)-H), 7.1-8.2 (m, 19 H, aromatic) 12g 1.17 (t, J = 7.0 Hz, 3 H, CH3CH20-), 2.20 (s, 3 H, C(3)-CH3), 4.10 (q, J = 7.0 Hz, 2 H, CH3CH20-), 4.63 (s, 2 H, C(2)-H2), 6.00 (s, 1 H, C(4)-H), 7.3 (m, 4 H, aromatic) 12h 2.15 (s, 3 H, C(3)-CH3), 6.02 (s, 1 H, C(4)-H), 6.50 H, aromatic) 12q 6.94 (s, 1 H, C(4)-Hc), 7.05-7.95 (m, 21 H, aromatic + C(2)--H) 12r 6.67 (s, 1 H, C(2)-H), 7.31-7.46 (m, 13 H, aromatic), 7.56-7.81 (m, aromatic ortho to C=0) + 7.59 (s, C(3)-H) -total 3 H 12s 1.6 (m, 4 H, -CH2CH2CH2CH2-), 2.3 (m, 4 H, -CH2CH2CH2CH2-), 6.78 (s, 1 H, C(2)-H), 7.15 (br s, 8 H, aromatic), 7.30 (s, 1 H, C(3)-H), 7.75 (m, 2 H, aromatic ortho to C=0) 12u 2.34 (m, 2 H, -CH2CH2OCH2-), 3.64 (br t, J s 5.5 Hz, 2 H, -CH2CH2OCH2-), 4.48 (br s, 2 H, -CH2CH2OCH2-), 6.95 (s, 1 H, C(2)-H), 7.11 (s, 8 H, aromatic), 7.27 4)-H may be reversed. for 29 h. After concentration in vacuo to ~20 mL, precipita...…”

“…We have methoxymercurated several partially resolved simple alienes and used a type Methoxymercuration of alienes with mercuric acetate in methanol usually affords both cis and trans adducts and is considered to occur by the mechanistic pathway shown in Scheme I. 3 This scheme predicts that the two adducts will be of opposite chirality. 3 Reaction of (R)-(-)-2,3-pentadiene (2), [«]25d -14.5°( 1, EÍ20), with Hg(OAc)2 in dry methanol at 25 °C followed by exchange of acetate for chloride affords a 6:1 ratio of trans:cis 3-chloromercuri-4-methoxy-2-pentenes, 3t and 3c, respectively.…”

“…3 This scheme predicts that the two adducts will be of opposite chirality. 3 Reaction of (R)-(-)-2,3-pentadiene (2), [«]25d -14.5°( 1, EÍ20), with Hg(OAc)2 in dry methanol at 25 °C followed by exchange of acetate for chloride affords a 6:1 ratio of trans:cis 3-chloromercuri-4-methoxy-2-pentenes, 3t and 3c, respectively. In CCI4 solution with 3 equiv of (R)-(-)-2,2,2-trifluoro-l-(9-anthryl)ethanol (la) the mixture of 3t and 3c shows NMR nonequivalence of the enantiotopic methoxyl resonances for each isomer.…”

An efficient synthesis of perhydro[1,2,4]triazolo[1,2-a][1,2,4]triazole-1,5-dithiones catalyzed by TiO2-functionalized nano-Fe3O4 encapsulated-silica particles as a reusable magnetic nanocatalyst

“…So, this conformation does not suffer the [4 + 2] cycloaddition known as the Diels-Alder reaction. 15 Although, there are a few papers in the literatures that have described the synthesis of perhydrotriazolotriazoledithione derivatives, they have drawbacks such as high catalyst loading, drastic conditions, low yields and long reaction times. 16,17 In recent decades, design of magnetically catalysts has attracted a great deal of attention due to simple separation of catalysts by a permanent magnetic eld.…”