New Cyano-Group-Containing 1,3-Oxaselenoles: Nucleophilic Substitution of a Cyano Group with Rearrangement

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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• 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. ¹H 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). ¹³C 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 C₁₈H₁₀N₂O₂Se: 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. ¹H 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). ¹³C 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 Al₂O₃, 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 Et₂O–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. ¹H NMR (400 MHz, DMSO-d ₆): δ = 7.24 (s, 1 H), 7.58 (m, 3 H), 7.78 (m, 2 H). ¹³C 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 C₁₁H₆N₂OSe: 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. ¹H 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). ¹³C 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 C₁₂H₈N₂O₂Se: 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, N₂H₄·H₂O, 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. ¹H 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). ¹³C 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. ¹H 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). ¹³C 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. ¹H 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). ¹³C 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. ¹H 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). ¹³C 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. ¹H 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). ¹³C 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. ¹H 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). ¹³C 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. ¹H 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). ¹³C 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. ¹H 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). ¹³C 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. ¹H 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). ¹³C 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. ¹H 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).¹³C 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.