ChemInform Abstract: Synthesis of Substituted Pyridines from Tetracyanoethylated Ketones and Hydrochloric or Hydrobromic Acid.

Насакин, О. Е.; Nikolaev, E. G.; Терентьев, П. Б.; Bulai, A. Kh.; Lavrent'eva, I. V.

doi:10.1002/chin.198750210

Cited by 3 publications

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“…12 The structures of the adducts 11 and 12 were confirmed by their cyclisation into pyridines and pyrans under the action of acids. 13 Acetylacetone 13a reacts with TCE in the presence of silver in benzene at room temperature to give easily cyclisable adduct 14a in 70% yield. 14 When the same compounds react in ethanol without a catalyst, the yield of 14a is 88%.…”

Section: Synthesis Of Michael Adductsmentioning

confidence: 99%

“…The adduct 12a synthesised from acetone and TCE cyclises into the 2H-pyran 139 under the action of hydrogen chloride. 13 The compounds 12, which are formed when ketones add to TCE (see Section III), can react with aldehydes at the terminal dicyanomethyl group; this yields bicyclic compounds with the pyran structure 140. 83 Refluxing of pyrazolones 41 with TCE in ethanol results in the formation of pyrano[2,3-c]pyrazoles 141.…”

Section: Synthesis Of Pyransmentioning

confidence: 99%

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Reactions of carbonyl compounds with α,β-unsaturated nitriles as a convenient pathway to carbo- and heterocycles

Sharanin¹,

Goncharenko²,

Литвинов³

1998

Russ. Chem. Rev.

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Abstrad.We re-examine the so-called Nambu-Iona-Lasinio mechanism suggested by Song, Xu and Chin in breaking the supersymmetry in the Wess-Zumino model and show that this mechanism cannot be justified without assuming special effects behveen fermions. The fermion condensation suggested by them corresponds to an mstable vacumm configuration and as a result there is no fermion condensation and no supersymmetg breaking in the model they discuss.

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Section: Synthesis Of Michael Adductsmentioning

confidence: 99%

Section: Synthesis Of Pyransmentioning

confidence: 99%

Reactions of carbonyl compounds with α,β-unsaturated nitriles as a convenient pathway to carbo- and heterocycles

Sharanin¹,

Goncharenko²,

Литвинов³

1998

Russ. Chem. Rev.

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“…It is also known that concentrated hydrochloric acid reacts with 4-oxoalkane-1,1,2,2-tetracarbonitriles to produce 2-chloropyridine-3,4-dicarbonitriles [3]. These data suggest that 2-chloropyridine-3,4-dicarbonitriles could be prepared via one-pot procedure, i.e., without isolation of 4-oxoalkane-1,1,2,2-tetracarbonitriles, which should make their preparation simpler and less expensive.…”

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confidence: 99%

“…When the reaction was complete (TLC), the mixture was diluted with water, and the precipitate was filtered off, washed with water and propan-2-ol, and recrystallized from propan-2-ol. Yield 0.85 g (89%), mp 72-74°C [3]. IR spectrum, ν, cm -1 : 2233 (C≡N), 1561, 1535 (C=C).…”

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confidence: 99%

Three-component synthesis of 2-chloropyridine-3,4-dicarbonitriles

et al. 2010

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SHORT COMMUNICATIONSAccording to published data, tetracyanoethylene reacts with ketones in the presence of a catalytic amount of hydrochloric acid to give 4-oxoalkane-1,1,2,2-tetracarbonitriles [1,2]. It is also known that concentrated hydrochloric acid reacts with 4-oxoalkane-1,1,2,2-tetracarbonitriles to produce 2-chloropyridine-3,4-dicarbonitriles [3]. These data suggest that 2-chloropyridine-3,4-dicarbonitriles could be prepared via one-pot procedure, i.e., without isolation of 4-oxoalkane-1,1,2,2-tetracarbonitriles, which should make their preparation simpler and less expensive.In fact, three-component reaction of tetracyanoethylene with the corresponding ketone Ia-If (aliphatic, aromatic, or heterocyclic) and hydrochloric acid in 1,4-dioxane afforded substituted 2-chloropyridine-3,4-dicarbonitriles IIa-IIf in 86-97% yield. The structure of compounds IIa-IIf was confirmed by IR, 1 H NMR, and mass spectra. ensured higher yield and shorter reaction time. Compounds IIb and IId-IIf were not reported previously.2-Chloro-5,6-dimethylpyridine-3,4-dicarbonitrile (IIa). Tetracyanoethylene, 0.64 g (0.005 mol), was added to a solution of 0.45 g (0.006 mol) of butan-2-one in 10 ml of 1,4-dioxane, 5 ml of concentrated hydrochloric acid was then added, and the mixture was stirred for 1-2 h at 60-70°C. When the reaction was complete (TLC), the mixture was diluted with water, and the precipitate was filtered off, washed with water and propan-2-ol, and recrystallized from propan-2-ol. Yield 0.85 g (89%), mp 72-74°C [3]. IR spectrum, ν, cm -1 : 2233 (C≡N), 1561, 1535 (C=C). 1 H NMR spectrum, δ, ppm: 2.56 s (3H, CH 3 ), 2.68 s (3H, CH 3 ). Mass spectrum: m/z 191 (I rel 57%). Found, %: C 55.98; H 3.15; N 21.58. C 9 H 6 ClN 3 . Calculated, %: C 56.41; H 3.16; N 21.93. M 191.62.Compounds IIb-IIf were synthesized in a similar way. 2-Chloro-5-ethyl-6-methylpyridine-3,4-dicarbonitrile (IIb). Yield 0.95 g (93%), mp 46-48°C. IR spectrum, ν, cm -1 : 2234 (C≡N), 1554 (C=C). 1 H NMR spectrum, δ, ppm: 1.19 t (3H, CH 3 , J = 8 Hz), 2.66 s (3H, CH 3 ), 2.86 q (2H, CH 2 , J = 8 Hz). Mass spectrum: m/z 205 (I rel 45%). Found, %: C 57.98; H 3.15; N 20.02. C 10 H 8 ClN 3 . Calculated, %: C 58.41; H 3.92; N 20.43. M 205.65. 2-Chloro-5,6,7,8-tetrahydroquinoline-3,4-dicarbonitrile (IIc). Yield 1.05 g (97%), mp 95-96°C [3]. IR spectrum, ν, cm -1 : 2222 (C≡N), 1539 (C=C). 1 H NMR spectrum, δ, ppm: 1.90 m (4H, CH 2 ), 2.89 t (2H, CH 2 , J = 6 Hz), 3.09 t (2H, CH 2 , J = 6 Hz). Mass spectrum: m/z 217 (I rel 100%). Found, %: C 59.96; R 1 = R 2 = Me (a); R 1 = Me, R 2 = Et (b); R 1 R 2 = (CH 2 ) 4 (c), (CH 2 ) 6 (d); R 1 = Ph, R 2 = H (e); R 1 = 2-thienyl, R 2 = H (f).

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“…Molecules of 5,6-dialkyl-2-halopyridine-3,4-dicarbonitriles [1][2][3][4] possess several reaction centers, namely halogen atom, cyano groups, and alkyl groups. The halogen atom in 2-halopyridine-3-carbonitriles is activated by the neighboring cyano group, and it can be readily replaced under mild conditions, e.g., by nitrogen-containing nucleophiles [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19].…”

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Regioselective reaction of 5,6-dialkyl-2-halopyridine-3,4-dicarbonitriles with ammonia

et al. 2012

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The reaction of 5,6-dialkyl-2-halopyridine-3,4-dicarbonitriles with alcoholic ammonia under elevated pressure gave 5,6-dialkyl-2-aminopyridine-3,4-dicarbonitriles as a result of nucleophilic replacement of the halogen atom by amino group. 6,7-Dialkyl-4-halo-1H-pyrrolo[3,4-c]pyridine-1,3(2H)-diimines were formed in analogous reaction at room temperature in the presence of potassium carbonate.II, R 1 = R 2 = Me (a), R 1 R 2 = (CH 2 ) 4 (b); I, III, R 1 = R 2 = Me, Hlg = Cl (a), Br (b), I (c); R 1 R 2 = (CH 2 ) 4 , Hlg = Cl (d), Br (e).Molecules of 5,6-dialkyl-2-halopyridine-3,4-dicarbonitriles [1-4] possess several reaction centers, namely halogen atom, cyano groups, and alkyl groups. The halogen atom in 2-halopyridine-3-carbonitriles is activated by the neighboring cyano group, and it can be readily replaced under mild conditions, e.g., by nitrogen-containing nucleophiles [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19]. Depending on the substrate and reagent nature, these transformations may be catalyzed by the reacting nucleophile [5,6] or other base such as potassium [7,8] or cesium carbonate [9, 10], sodium hydrogen carbonate [11,12], triethylamine [13,14], ethyl(diisopropyl)amine [15,16], etc. Taking into account reduced nucleophilicity and high volatility of ammonia compared to primary and secondary amines, 2-aminopyridine-3-carbonitriles are synthesized under pressure [12,17, 18] or microwave irradiation [19].The halogen atom in 5,6-dialkyl-2-halopyridine-3,4-dicarbonitriles Ia-Ie was not replaced by amino group on prolonged heating in aqueous ammonia or in organic solvents saturated with ammonia (ethanol, propan-2-ol, 1,4-dioxane, acetonitrile). We succeeded in obtaining 5,6-dialkyl-2-aminopyridine-3,4-dicarbonitriles IIa and IIb in 72-82% yield by carrying out the reaction under elevated pressure in ethanol saturated with ammonia (Scheme 1). Replacement of the chlorine atom in compounds Ia and Id by amino group required a shorter time than analogous reactions with bromo-and iodo-substituted derivatives Ib, Ic, and Ie. Presumably, the formation of the corresponding intermediate from chloropyridine derivatives is more favorable for steric reasons, as well as from the viewpoint of its better stabilization due to higher electronegativity of chlorine as compared to bromine and iodine. The observed pattern is consistent with the assumed addition-elimination mechanism of aromatic nucleophilic replacement (S N Ar).With a view to accelerate halogen replacement in 5,6-dialkyl-2-halopyridine-3,4-dicarbonitriles Ia-Ie in the reaction with ammonia, we added potassium carbonate to the reaction mixture. The use of K 2 CO 3 as catalyst in nucleophilic substitution reactions of 2-halopyridine-3-carbonitriles with various amines was reported in [7,8]. However, the reaction of compounds NH HN NH Scheme 1.

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ChemInform Abstract: Synthesis of Substituted Pyridines from Tetracyanoethylated Ketones and Hydrochloric or Hydrobromic Acid.

Abstract: Treatment of tetracyanoethylated ketones (I) with hydrochloric or hydrobromic acid results in the formation of the dicyanopyridines (III).

Cited by 3 publications

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Reactions of carbonyl compounds with α,β-unsaturated nitriles as a convenient pathway to carbo- and heterocycles

Reactions of carbonyl compounds with α,β-unsaturated nitriles as a convenient pathway to carbo- and heterocycles

Three-component synthesis of 2-chloropyridine-3,4-dicarbonitriles

Regioselective reaction of 5,6-dialkyl-2-halopyridine-3,4-dicarbonitriles with ammonia

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