Synlett 2018; 29(15): 2035-2038
© Georg Thieme Verlag Stuttgart · New York
New Cyano-Group-Containing 1,3-Oxaselenoles: Nucleophilic Substitution of a Cyano Group with Rearrangement
Andrey V. Kachanov*
a
Far Eastern Federal University, School of Natural Sciences, Sukhanov Str., 8, Vladivostok 690950, Russian Federation Email:
kachanov.av@dvfu.ru
,
Andrey V. Zamaraev
b
G. B. Elyakov Pacific Institute of Bioorganic Chemistry, Far East Branch of the Russian Academy of Sciences, prospect 100 let Vladivostoku, 159, Vladivostok 690022, Russian Federation
,
Andrey V. Gerasimenko
c
Institute of Chemistry, Far East Branch of the Russian Academy of Sciences, prospect 100 let Vladivostoku, 159, Vladivostok 690022, Russian Federation
,
Konstantin V. Maslov
a
Far Eastern Federal University, School of Natural Sciences, Sukhanov Str., 8, Vladivostok 690950, Russian Federation Email:
kachanov.av@dvfu.ru
,
Oleg Yu. Slabko
a
Far Eastern Federal University, School of Natural Sciences, Sukhanov Str., 8, Vladivostok 690950, Russian Federation Email:
kachanov.av@dvfu.ru
,
Vladimir A. Kaminskii
a
Far Eastern Federal University, School of Natural Sciences, Sukhanov Str., 8, Vladivostok 690950, Russian Federation Email:
kachanov.av@dvfu.ru
› Author Affiliations
Abstract
New cyano-group-containing 1,3-oxaselenoles were obtained by the treatment of aroylacetonitriles with selenium(IV) oxide. The resulting products were shown to react with ammonia, hydrazine, or primary amines; this reaction was accompanied by aryl rearrangement.
Key words aroylacetonitriles - selenium oxide - oxaselenoles - nucleophilic substitution - rearrangement
References and Notes
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Hartmann H.
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Kachanov AV.
Slabko OYu.
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Kaminskii VA.
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7
Baba A.
Yasuma T.
Tawada H.
Yamashita M.
WO 2005111046, 2005
8
2-Aroyl-1,3-oxaselenole-2,4-dicarbonitriles 3 and 4: General Procedure
The appropriate aroylacetonitrile 1 or 2 (34 mmol) and SeO2 (5.66 g, 51 mmol) were added successively, with stirring, to toluene (100 mL), and the mixture was heated to boiling for 5 h until the reaction was complete (TLC). During the reaction, the color of the mixture changed from yellow to dark-red, and a small amount of gray selenium precipitated. The solution was then decanted and the solvent was evaporated to give an oily residue that was dried under reduced pressure. If necessary, the product could be purified chromatographically (silica gel, DCE).
2-Benzoyl-5-phenyl-1,3-oxaselenole-2,4-dicarbonitrile (3)
Red oil; yield: 5.03 g (81%). IR (KBr): 3067, 2206, 1701, 1597 cm–1 . 1 H NMR (400 MHz, DMSO-d
6 ): δ = 7.57–7.66 (m, 5 H), 7.76 (t, J = 7.4 Hz, 1 H), 7.90 (d, J = 8.5 Hz, 2 H), 8.13 (d, J = 8.5 Hz, 2 H). 13 C NMR (100 MHz, DMSO-d
6 ): δ = 45.2, 79.6, 114.4, 116.0, 126.6, 127.9, 129.2, 129.3, 129.7, 130.2, 132.5, 135.0, 160.8, 183.8. LC/MS (APCI): m/z [M+ ] calcd for C18 H10 N2 O2 Se: 365.99; found: 365.98.
2-(4-Methoxybenzoyl)-5-(4-methoxyphenyl)-1,3-oxaselenole-2,4-dicarbonitrile (4)
Orange solid; yield: 5.57 g (77%); mp 122–124 °C. IR (KBr): 3076, 2843, 2205, 1655, 1593 cm–1 . 1 H NMR (400 MHz, DMSO-d
6 ): δ = 3.85 (s, 3 H), 3.88 (s, 3 H), 7.14 (d, J = 9.0 Hz, 4 H), 7.87 (d, J = 9.0 Hz, 2 H), 8.12 (d, J = 9.0 Hz, 2 H). 13 C NMR (100 MHz, DMSO-d
6 ): δ = 55.7, 55.9, 76.5, 79.20, 114.6, 114.7, 114.9, 116.2, 118.8, 122.5, 130.0, 132.4, 160.8, 162.3, 164.6, 182.4.
9 CCDC 1824131 and 1824130 contain the supplementary crystallographic data for compounds 4 and 7c , respectively. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
10
1,3-Oxaselenole-2,4-dicarbonitriles 5 and 6; General Method
The appropriate oxaselenole 3 or 4 (300.0 mg) was applied to a chromatographic plate measuring 250 × 300 mm with an unattached layer of Al2 O3 , and was eluted four times with DCE. During the chromatography, dearoylation occurred and the color of the upper spot changed from yellow to pale yellow. Part of the upper area was collected and extracted with DCE. The solvent was evaporated and the semi-solid residue was dissolved in an Et2 O–hexane mixture. The resulting solution was slowly evaporated at r.t. over a few days. The resulting crystals were separated and dried under reduced pressure.
5-Phenyl-1,3-oxaselenole-2,4-dicarbonitrile (5)
Gray solid; yield: 50.0 mg (24%); mp 78–79 °C. IR (KBr): 2997, 2206, 1595 cm–1 . 1 H NMR (400 MHz, DMSO-d
6 ): δ = 7.24 (s, 1 H), 7.58 (m, 3 H), 7.78 (m, 2 H). 13 C NMR (100 MHz, DMSO-d
6 ): δ = 65.4, 77.7, 114.9, 117.5, 127.0, 127.3, 129.4, 132.2, 161.3. GC/MS: m/z [M+ ] calcd for C11 H6 N2 OSe: 261.97, found: 262.00.
5-(4-Methoxyphenyl)-1,3-oxaselenole-2,4-dicarbonitrile (6)
Gray solid; yield: 70.0 mg (33%); mp 100–101 °C. IR (KBr): 2934, 2839, 2195, 1607 cm–1 . 1 H NMR (400 MHz, DMSO-d
6 ): δ = 3.83 (s, 3 H), 7.11 (d, J = 9.0 Hz, 2 H), 7.20 (s, 1 H), 7.76 (d, J = 9.0 Hz, 2 H). 13 C NMR (100 MHz, DMSO-d
6 ): δ = 55.7, 65.0, 74.6, 114.8, 115.4, 117.6, 119.3, 129.3, 161.3, 162.1. GC/MS: m/z [M+ ] calcd for C12 H8 N2 O2 Se: 291.98, found: 292.00.
11
Replacement Products 7a –e and 8a –e; General Procedure
A solution of the appropriate oxaselenole 3 or 4 (1.6 mmol) in EtOH or MeCN (3 mL) was cooled and aq NH3 , N2 H4 ·H2 O, or a primary amine was added with stirring. After 2 h, the product spontaneously precipitated as an amorphous precipitate that was collected by filtration, washed once with the cooled solvent, and dried. The resulting product was crystallized from the appropriate solvent.
4-Cyano-2,5-diphenyl-1,3-oxaselenole-2-carboxamide (7a)
White solid; yield: 227.3 mg (40%); mp 207–208 °C (THF–hexane). IR (KBr): 3393, 3312, 3061, 2210, 1674, 1593 cm–1 . 1 H NMR (400 MHz, DMSO-d
6 ): δ = 7.41–7.47 (m, 3 H), 7.56–7.62 (m, 3 H), 7.64 (d, J = 7.7 Hz, 1 H), 7.65 (d, J = 8.2 Hz, 1 H), 7.99 (s, 1 H), 8.13 (d, J = 8.0 Hz, 1 H), 8.14 (d, J = 7.3 Hz, 1 H), 8.21 (s, 1 H). 13 C NMR (100 MHz, DMSO-d
6 ): δ = 75.2, 97.7, 115.1, 125.1, 127.4, 127.5, 128.6, 129.2, 129.6, 131.9, 139.6, 160.4, 170.1.
4-Cyano-2,5-diphenyl-1,3-oxaselenole-2-carbohydrazide (7b)
White solid; yield: 335.1 mg (57%); mp 184–185 °C (toluene). IR (KBr): 3325, 3275, 3063, 2199, 1663, 1597 cm–1 . 1 H NMR (400 MHz, DMSO-d
6 ): δ = 4.58 (s, 2 H), 7.40–7.46 (m, 3 H), 7.57–7.61 (m, 3 H), 7.63 (d, J = 7.8 Hz, 1 H), 7.64 (d, J = 8.3 Hz, 1 H), 8.17 (d, J = 8.0 Hz, 1 H), 8.18 (d, J = 7.3 Hz, 1 H), 10.06 (s, 1 H). 13 C NMR (100 MHz, DMSO-d
6 ): δ = 75.2, 97.4, 115.1, 125.0, 127.4, 127.5, 128.6, 129.2, 129.7, 131.9, 139.8, 160.4, 166.9.
N -Benzyl-4-cyano-2,5-diphenyl-1,3-oxaselenole-2-carboxamide (7c)
White solid; yield: 299.0 mg (42%); mp 169–170 °C (toluene). IR (KBr): 3312, 3065, 2851, 2205, 1659, 1593 cm–1 . 1 H NMR (400 MHz, DMSO-d
6 ): δ = 4.36 (m, 2 H), 7.15–7.29 (m, 5 H), 7.41–7.48 (m, 3 H), 7.57–7.63 (m, 3 H), 7.66 (d, J = 7.4 Hz, 1 H), 7.67 (d, J = 8.0 Hz, 1 H), 8.12 (d, J = 7.9 Hz, 1 H), 8.13 (d, J = 7.1 Hz, 1 H), 9.31 (t, J = 6.1 Hz, 1 H). 13 C NMR (100 MHz, DMSO-d
6 ): δ = 42.5, 75.4, 97.4, 115.0, 125.1, 127.0, 127.1, 127.4, 128.4, 128.7, 129.2, 129.7, 131.9, 138.7, 139.5, 160.5, 168.2.
4-Cyano-N -(4-tolyl)-2,5-diphenyl-1,3-oxaselenole-2-carboxamide (7d)
White solid; yield: 315.7 mg (44%); 145–146 °C (EtOH). IR (KBr): 3331, 3055, 2920, 2201, 1663, 1595 cm–1 . 1 H NMR (400 MHz, DMSO-d
6 ): δ = 2.25 (s, 3 H), 7.15 (d, J = 8.3 Hz, 2 H), 7.45–7.51 (m, 5 H), 7.60–7.64 (m, 3 H), 7.73 (d, J = 8.0 Hz, 1 H), 7.74 (d, J = 8.4 Hz, 1 H), 8.13–8.16 (m, 2 H), 10.31 (s, 1 H). 13 C NMR (100 MHz, DMSO-d
6 ): δ = 20.5, 75.6, 97.8, 115.1, 121.2, 125.7, 127.5, 127.6, 128.8, 129.2, 129.9, 131.9, 134.1, 134.8, 138.9, 160.6, 166.7.
4-Cyano-N -(4-methoxyphenyl)-2,5-diphenyl-1,3-oxaselenole-2-carboxamide (7e)
White solid; yield: 274.0 mg (37%); 123–124 °C (EtOH). IR (KBr): 3315, 3061, 2833, 2203, 1657, 1597 cm–1 . 1 H NMR (400 MHz, DMSO-d
6 ): δ = 3.72 (s, 3 H), 6.91 (d, J = 9.1 Hz, 2 H), 7.45–7.51 (m, 5 H), 7.60–7.63 (m, 3 H), 7.73 (d, J = 7.8 Hz, 1 H), 7.74 (d, J = 8.2 Hz, 1 H), 8.14–8.16 (m, 2 H), 10.29 (s, 1 H). 13 C NMR (100 MHz, DMSO-d
6 ): δ = 55.3, 75.6, 97.8, 113.9, 115.1, 122.9, 125.6, 127.5, 127.6, 128.8, 129.2, 129.9, 130.2, 131.9, 139.0, 156.4, 160.6, 166.5.
4-Cyano-2,5-bis(4-methoxyphenyl)-1,3-oxaselenole-2-carboxamide (8a)
Pale-yellow solid; yield: 299.5 mg (45%); 184–185 °C (EtOH). IR (KBr): 3495, 3331, 2935, 2837, 2199, 1691, 1605 cm–1 . 1 H NMR (400 MHz, DMSO-d
6 ): δ = 3.74 (s, 3 H), 3.84 (s, 3 H), 6.98 (d, J = 9.0 Hz, 2 H), 7.12 (d, J = 9.0 Hz, 2 H), 7.55 (d, J = 8.9 Hz, 2 H), 7.91 (s, 1 H), 8.09 (d, J = 9.0 Hz, 2 H), 8.15 (s, 1 H). 13 C NMR (100 MHz, DMSO-d
6 ): δ = 55.4, 55.7, 72.2, 97.7, 113.9, 114.6, 115.7, 120.1, 126.7, 129.4, 131.4, 160.2, 160.6, 161.9, 170.4.
4-Cyano-2,5-bis(4-methoxyphenyl)-1,3-oxaselenole-2-carbohydrazide (8b)
Pale-yellow solid; yield: 344.2 mg (50%); 106–108 °C (toluene). IR (KBr): 3352, 3323, 2935, 2839, 2201, 1670, 1607 cm–1 . 1 H NMR (400 MHz, DMSO-d
6 ): δ = 3.74 (s, 3 H), 3.85 (s, 3 H), 4.55 (s, 2 H); 6.97 (d, J = 8.9 Hz, 2 H), 7.12 (d, J = 8.9 Hz, 2 H), 7.54 (d, J = 8.9 Hz, 2 H), 8.13 (d, J = 8.9 Hz, 2 H), 10.00 (s, 1 H). 13 C NMR (100 MHz, DMSO-d
6 ): δ = 55.4, 55.7, 72.2, 97.4, 113.9, 114.6, 115.7, 120.0, 126.6, 129.5, 131.5, 160.2, 160.6, 161.9, 167.1.
N -Benzyl-4-cyano-2,5-bis(4-methoxyphenyl)-1,3-oxaselenole-2-carboxamide (8c)
Pale-yellow solid; yield: 336.6 mg (42%); 133–134 °C (toluene). IR (KBr): 3319, 2930, 2837, 2197, 1653, 1607 cm–1 . 1 H NMR (400 MHz, DMSO-d
6 ): δ = 3.75 (s, 3 H), 3.84 (s, 3 H), 4.35 (qd, J = 15.3, 6.2 Hz, 2 H), 6.99 (d, J = 9.0 Hz, 2 H), 7.13 (d, J = 9.0 Hz, 2 H), 7.17–7.30 (m, 5 H), 7.57 (d, J = 8.8 Hz, 2 H), 8.08 (d, J = 9.0 Hz, 2 H), 9.25 (t, J = 6.2 Hz, 1 H). 13 C NMR (100 MHz, DMSO-d
6 ): δ = 42.5, 55.4, 55.7, 72.4, 97.4, 114.0, 114.6, 115.7, 120.0, 126.8, 127.0, 128.4, 129.5, 131.2, 138.8, 160.2, 160.6, 161.9, 168.4.
4-Cyano-2,5-bis(4-methoxyphenyl)-N -(4-tolyl)-1,3-oxaselenole-2-carboxamide (8d)
White solid; yield: 490.6 mg (61%); 158–161 °C (EtOH). IR (KBr): 3330, 3055, 2201, 1663, 1595 cm–1 . 1 H NMR (400 MHz, DMSO-d
6 ): δ = 2.25 (s, 3 H), 3.75 (s, 3 H), 3.85 (s, 3 H), 7.02 (d, J = 8.9 Hz, 2 H), 7.15 (d, J = 8.9 Hz, 4 H), 7.46 (d, J = 8.5 Hz, 2 H), 7.63 (d, J = 8.9 Hz, 2 H), 8.11 (d, J = 9.0 Hz, 2 H), 10.26 (s, 1 H). 13 C NMR (100 MHz, DMSO-d
6 ): δ = 20.6, 55.5, 55.7, 72.7, 97.8, 113.7, 114.1, 114.6, 115.7, 120.1, 121.2, 127.4, 129.3, 129.7, 130.5, 134.9, 160.4, 160.9, 162.0, 167.0.
4-Cyano-N ,2,5-tris(4-methoxyphenyl)-1,3-oxaselenole-2-carboxamide (8e)
Yellow solid; yield: 454.1 mg (54%); 212–214 °C (EtOH–1,4-dioxane). IR (KBr): 3306, 2932, 2835, 2199, 1664, 1607 cm–1 . 1 H NMR (400 MHz, DMSO-d
6 ): δ = 3.72 (s, 3 H), 3.75 (s, 3 H), 3.85 (s, 3 H), 6.91 (d, J = 9.0 Hz, 2 H), 7.02 (d, J = 8.9 Hz, 2 H), 7.14 (d, J = 9.0 Hz, 2 H), 7.48 (d, J = 9.1 Hz, 2 H), 7.63 (d, J = 8.9 Hz, 2 H), 8.11 (d, J = 8.9 Hz, 2 H), 10.23 (s, 1 H).13 C NMR (100 MHz, DMSO-d
6 ): δ = 55.3, 55.5, 55.7, 72.6, 97.8, 113.7, 114.0, 114.1, 114.6, 115.7, 120.1, 122.9, 127.3, 129.7, 130.7, 156.4, 160.4, 160.9, 162.0, 166.8.
