ChemInform Abstract: REACTION OF TETRACYANOETHYLENE WITH METHYL ALKYL KETONES

Nikolaev, E. G.; Насакин, О. Е.; Терентьев, П. Б.; Khaskin, B. A.; Петров, В.Г.

doi:10.1002/chin.198419144

Cited by 4 publications

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“…3,4 It has been found that reaction of TCE 9a with ketones 10 catalysed by `molecular silver' or alcohols occurs selectively involving the methyl group and yields acyclic adducts 11. 12 To activate the methylene group and obtain the isomeric product 12, the reaction needs to be conducted with heating in the presence of acetic or trichloroacetic acid. 12 The structures of the adducts 11 and 12 were confirmed by their cyclisation into pyridines and pyrans under the action of acids.…”

Section: Synthesis Of Michael Adductsmentioning

confidence: 99%

“…12 To activate the methylene group and obtain the isomeric product 12, the reaction needs to be conducted with heating in the presence of acetic or trichloroacetic acid. 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.…”

Section: Synthesis Of Michael Adductsmentioning

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 Michael Adductsmentioning

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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“…According 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].…”

Section: Short Communicationsmentioning

confidence: 95%

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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“…It is known that reactions of tetracyanoethylene with ketones in the presence of hydrochloric acid involve mainly the α-branched CH unit with respect to the oxo group [5]. However, in some cases tetracyanoethylene adds at the less substituted carbon atom due to steric factor, as was shown in the reaction with menthone as an example [6].…”

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confidence: 93%

Reactions of pregnenolone and 16-dehydropregnenolone acetate with tetracyanoethylene

et al. 2010

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ChemInform Abstract: REACTION OF TETRACYANOETHYLENE WITH METHYL ALKYL KETONES

Abstract: Tetracyanethylen (I) reagiert mit den Methylketonen (I l) in Gegenwart von Alkoholen als Katalysatoren an der Methylgruppe der Ketone (II) zu den Tetracyanketonen (III).

Cited by 4 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

Reactions of pregnenolone and 16-dehydropregnenolone acetate with tetracyanoethylene

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