Reaction of Tetracyanoethylated Cyclohexanones with ... - Springer Link

2 downloads 0 Views 163KB Size Report
Belikov, O. V. Ershov, A. V. Eremkin, Ya. S. Kayukov, and O. E. Nasakin. Ul'yanov Chuvash State University, Moskovskii pr. 15, Cheboksary, 428015 Russia.
ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 10, pp. 2078–2080. © Pleiades Publishing, Ltd., 2010. Original Russian Text © M.Yu. Belikov, O.V. Ershov, A.V. Eremkin, Ya.S. Kayukov, O.E. Nasakin, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 10, pp. 1757–1758.

LETTERS TO THE EDITOR

Reaction of Tetracyanoethylated Cyclohexanones with Water in Acidic Medium M. Yu. Belikov, O. V. Ershov, A. V. Eremkin, Ya. S. Kayukov, and O. E. Nasakin Ul’yanov Chuvash State University, Moskovskii pr. 15, Cheboksary, 428015 Russia e-mail: [email protected] Received February 18, 2010

DOI: 10.1134/S1070363210100373 oxopentane-1,1,2,2-tetracarbonitrile to afford 5,6-dimethyl-2-oxo-1,2-dihydropyridine-3,4-dicarbonitrile in 10% yield has been reported [3].

It was reported earlier that 4-oxoalkane-1,1,2,2tetracarbonitriles depending on different factors react with hydrohalic acids to form 2-halopyridine-3,4dicarbonitriles [1–3], 2-halo-6-hydroxy-5,6-dihydroxypyridine-3,4,4(1Н)-tricarbonitriles [4], pyrrolo[3,4-c] pyrrole-1,3,4,6(2H,3аH,5H,6аH)-tetraones [1], 3-halo6-oxo-2,7-diazabicyclo[3.2.1]oct-3-ene-4,5-dicarbonitriles [5]. At the same time the influence of the structure of 4-oxoalkane-1,1,2,2-tetracarbonitriles on the reaction with aqueous sulfuric acid was not studied. Only reaction of 50% sulfuric acid with 3-methyl-4-

2

R

2

R

R1

NC CN

O Iа_Ic

CN

+H2O

R1

We found a possibility of realization of various directions of the reaction of tetracyanoethylated cyclohexanones Ia–Ic with 90% aqueous sulfuric acid depending on the substituent R1 in the position 3. Thus, nitriles Iа and Ib were found to react affording the earlier unknown 2-oxo-1,2,5,6,7,8-hexahydroquinoline3,4-dicarbonitriles IIа and IIb.

NC CN

N H

HO

CN CN

O 2

A

_ _

CN _

H2O, HCN

R

CN N O H IIа, IIb

H 2O

NC CN H3C

N H

CN O

IIc R1 = H, R2 = Me (а); R1 = H, R2 = t-Bu (b); R1 = Me, R2 = H (c).

2078

REACTION OF TETRACYANOETHYLATED CYCLOHEXANONES

Apparently, in these processes hydroxy derivative A is the key intermediate. Its formation is a result of the acid-catalyzed attack of water on compounds Iа and Ib followed by the generation of the hydrogenated pyridine ring. Then, water is eliminated from A by the action of concentrated sulfuric acid followed by hydrogen cyanide removal to give pyridines IIа and IIb. Aiming to change the direction of А transformation, we used in the reaction with water tetracyanoalkanone Ic, in which the transformation А → IIa, Ib is impossible due to the presence of methyl group. In this case under similar condition the reaction product of another structure, 4a-methyl-2-oxo1,2,3,4,4a,5,6,7-octahydroquinoline-3,4-dicarbonitrile IIc, was obtained. We believe that in this case the reaction proceeds through the derivative А formation, but the hydrogen cyanide elimination does not occur by the way described for the synthesis of IIа and IIb, and the analog of the products mentioned above is not formed. As a result, water is eliminated resulting in the structure IIc. The structure of compounds IIa–IIc was proved by IR, 1Н NMR spectroscopy, mass spec-trometry, and elemental analysis. General procedure for the synthesis of compounds IIa–IIc. 0.001 mol of the corresponding 1-(2oxocyclohexyl)ethane-1,1,2,2-tetracarbonitrile Ia–Ic was dissolved in 5 ml of THF–1,4-dioxane mixture (4:1) at room temperature. To this solution 1 ml of 90% sulfuric acid was added. The reaction mixture warmed up. Then it was kept for 3–4 h at room temperature, poured into crushed ice under stirring to form yellow precipitate. The latter was filtered off, washed with cold water, 2-propanol, and dried in a vacuum to the constant mass. 6-Methyl-2-oxo-1,2,5,6,7,8-hexahydroquinoline3,4-dicarbonitrile (IIа) was obtained from 0.240 g of 1-(5-methyl-2-oxocyclohexyl)ethane-1,1,2,2-tetracarbonitrile Ia. Yield 0.158 g (74%), mp 205–207°С. IR spectrum, ν, cm–1: 2212 (С≡N), 1716 (C=O). 1Н NMR spectrum, δ, ppm (J, Hz): 1.03 d (3Н, СH3, J 6.5), 1.28–1.37 m (1H, CHCH3), 1.76–1.83 m (2H, CHCH2CH2), 2.12–2.18 d.d (1H, CHCH2, J 10.4, J 15.9), 2.64–2.67 m (1H, CHCH2), 2.68–2.71 m (2H,

2079

CHCH2CH2), 13.15 br.s (1H, NH). Mass spectrum, m/z (Irel, %): 213 (12) [M]+. Found, %: C 67.70; H 5.12; N 19.62. C12H11N3O. Calculated, %: C 67.59; H 5.20; N 19.71. 6-tert-Butyl-2-oxo-1,2,5,6,7,8-hexahydroquinoline3,4-dicarbonitrile (IIb) was obtained from 0.282 g of 1-(5-tert-butyl-2-oxocyclohexyl)ethane-1,1,2,2-tetracarbonitrile Ib. Yield 0.179 g (70%), mp 153–154°С. IR spectrum, ν, cm–1 : 2215 (С≡N), 1719 (C=O). 1Н NMR spectrum, δ, ppm (J, Hz): 0.92 s (9Н, t-Bu), 1.23–1.27 m (1Н, CHCH2CH2), 1.37–1.41 m (1Н, CHCH2CH2), 1.93–1.97 m (1Н, t-BuCH), 2.26–2.32 d.d (1Н, CHCH2, J 12.1, J 15.5), 2.72–2.78 m (1Н, CHCH2), 2.60–2.69 m (2Н, CHCH2CH2), 13.10 br.s (1H, NH). Mass spectrum, m/z (Irel, %): 255 (19) [M]+. Found, %: C 70.64; H 6.63; N 16.37. C15H17N3O. Calculated, %: C 70.56; H 6.71; N 16.46. 4а-Methyl-2-oxo-1,2,3,4,4а,5,6,7-octahydroquinoline-3,4-dicarbonitrile (IIc) was obtained from 0.240 g 1-(1-methyl-2-oxocyclohexyl)ethane-1,1,2,2tetracarbonitrile Ic. Yield 0.161 g (67%), mp 219–220°С. IR spectrum, ν, cm–1 : 2251 (С≡N), 1731 (С=O). 1Н NMR spectrum, δ, ppm (J, Hz): 1.37 s (3H, CH3), 1.65–1.99 m (4Н, 2CH2), 2.04–2.14 m (2Н, =CHCH2), 5.42–5.45 d.d (1Н, =CH, J 2.9, J 5.0), 5.92 s (1H, CHCN), 10.88 s (1Н, NH). Mass spectrum, m/z (Irel, %): 240 (7) [M]+. Found, %: C 65.07; H 4.96; N 23.25. C13H12N4O. Calculated, %: C 64.99; H 5.03; N 23.32. Reaction progress and purity of the obtained compounds was monitored by TLC on “Silufol UV-254” plates detecting with UV irradiation, iodine vapor, or thermal decomposition. The IR spectra were recorded on an IR Fourier-spectrometer FSМ-1202 from thin film (or suspension in mineral oil). The 1Н NMR spectra were registered on a Bruker DRX–500 spectrometer, operating frequency 500.13 MHz, solvent DMSO-d6, internal reference TMS. The mass spectra were registered on a Finnigan МАТ.INCOS 50 instrument (EI, 70 eV). ACKNOWLEDGMENTS This work was financially supported by the Russian Foundation for Basic Research (project no. 10-0397013-р_povolzh’e_а).

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 10 2010

2080

BELIKOV et al.

REFERENCES 1. Ershov, O.V., Lipin, K.V., Maksimova, V.N., Eremkin, A.V., Kayukov, Ya.S., and Nasakin, O.E., Zh. Org. Khim., 2009, vol. 45, no. 3, p. 484. 2. Nasakin, O.E., Nikolaev, E.G., Terent’ev, P.B., Bulay, A.Kh., Khaskin, B.A., and Mikhailov, V.K., Khim. Geterotsikl. Soedin., 1984, no. 11, p. 1547.

3. Nasakin, O.E., Nikolaev, E.G., Terent’ev, P.B., Bulay, A.Kh., and Lavrent’eva, I.V., Khim. Geterotsikl. Soedin., 1987, no. 5, p. 653. 4. Sheverdov, V.P., Ershov, O.V., Nasakin, O.E., Chernushkin, A.N., and Tafeenko, V.A., Zh. Org. Khim., 2002, vol. 38, no. 7, p. 1043. 5. Lipin, K.V., Candidate Sci. (Chem.) Dissertation, Kazan, 2009.

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 10 2010