Pseudo Five-Component Reaction of Isocyanides,Dialkylacetylenedicarboxylates, and 2,3

Pseudo five-component reaction of isocyanides,Dialkylacetylenedicarboxylates, and 2,3- dichloronaphthalene-1,4-dione: A highly

diastereocelective synthesis of novel dispirofuran-2,1'-naphthalenes

Hamed Rouhi Sadabad,a Ayoob Bazgir,a Mohammad Eskandari,b Ramin Ghahremanzadeh,*b

aDepartment of Chemistry, ShahidBeheshti University, General Campus, Tehran, Iran.

bNanobiotechnology Research Center, Avicenna Research Institute, ACECR, Tehran, Iran. E.mail:

SUPPORTING INFORMATION

Experimental Part

General procedure for the synthesis of compounds. Melting points were measured on an Elecrtothermal 9100 apparatus and are uncorrected. Mass spectra were recorded on a shimadzuShimadzu QP 1100 Ex mass spectrometer operating at an ionization potential of 70 eV. 1H and 13C NMR spectra were recorded on a BRUKER DRX-300 AVANCE spectrometer at 300.13 and 75.47 MHz, respectively. 1H and 13C NMR spectra were obtained on solutions in CDCl3 and DMSO-d6 using TMS as internal standard. IR spectra were recorded using an FTIR apparatus. Elemental analyses were performed using a Heracus CHN-O-Rapid analyzer.

The chemical used in this work were obtained from Fluka and Merck and were used without purification.

Typical procedure for the preparation of 2',3'-dichloro-bis(dimethyl-5-(tert-butylimino)-4'H,5H)dispiro [furan-2,1'-naphthalene]-3,3',4,4'-tetra-carboxylate (4a):

To a magnetically stirred solution of 2,3-dichloronaphthalene-1,4-dione (0.23 g, 1.0 mmol) and dimethylacetylenedicarboxylate (0.28 g, 2.0 mmol) in CH3CN (10 cm3) was added dropwise to a solution of tert-butyl isocyanide (0.16 g, 2 mmol) in CH3CN (2 cm3) at room temperature over 10 min. The mixture was stirred for 24 h. Then, the reaction mixture was filtered off and the residue was washed with ether (10 cm3) and then residue recrystallized from EtOH to afford the pure product 4a.

Yield: 96 %; White powder; M.p.: 240-242 ˚C. IR (KBr): = 2972, 1755, 1734, 1686 cm–1. MS (EI, 70eV) m/z: 676 (M+). 1H NMR (300 MHz, CDCl3): δ = 1.31 (s, 18H, 2C(Me)3), 3.61 (s, 6H, 2OMe), 3.98 (s, 6H, 2OMe), 7.22-7.45 (m, 4H, H-Ar)ppm. 13C NMR (75.47 MHz, CDCl3)δ = 29.4, 52.6, 53.2, 55.3, 86.8, 126.5, 130.1, 131.6, 131.9, 140.4, 142.2, 151.9, 159.4, 162.0. Anal.Calcd.for C32H34Cl2N2O10.: C, 56.73; H, 5.06; N, 4.13. found: C, 56.62; H, 5.01; N, 4.20%.

2',3'-Dichloro-bis(diethyl-5-(tert-butylimino)-4'H,5H)dispiro[furan-2,1'-naphthalene]-3,3',4,4'-tetra-carboxylate (4b):

Yield:92%; white powder; M.p.: 198-200 ºC. IR (KBr): = 2988, 2925, 1757, 1726, 1684 cm-1. MS (EI, 70eV) m/z: 732 (M+). 1H NMR (300 MHz, CDCl3): δ = 1.02 (t, 3JHH =6.9 Hz, 6H,2CH3), 1.29 (s, 18H, 2C(Me)3), 1.40 (t, 3JHH =7.0 Hz, 6H, 2CH3), 4.08 (q, 3JHH =7.0 Hz, 4H, 2CH2), 4.51 (q, 3JHH=7.0 Hz, 4H, 2CH2), 7.23-7.44 (m, 4H, H-Ar). 13C NMR (75.47 MHz, CDCl3): δ = 13.8, 14.1, 29.4, 55.1, 61.6, 62.3, 76.6, 77.0, 77.5, 86.9, 126.5, 129.9, 131.8, 132.0, 140.0, 142.2, 152.0, 159.0, 161.6. Anal.Calcd.for C36H42Cl2N2O10: C, 58.94; H, 5.77; N, 3.82%. found: C, 58.82; H, 5.83; N, 3.76%.

2',3'-Dichloro-bis(dimethyl-5-(cyclohexylimino)-4'H,5H)dispiro[furan-2,1'-naphthalene]-3,3',4,4'-tetra-carboxylate (4c):

Yield:95%; White powder; M.p.: 258-260 ºC. IR (KBr): = 2935, 2859, 1757, 1738, 1687 cm-1. MS (EI, 70eV) m/z: 728 (M+). 1H NMR (300 MHz, DMSO-d6): δ = 1.18-1.67 (m, 20H, 2Cy), 3.54 (m, 2H, CHN), 3.60 (s, 6H, 2OCH3), 3.91 (s, 6H, 2OCH3), 7.15-7.63 (m, 4H, H-Ar). 13C NMR (75.47 MHz, DMSO-d6): δ = 23.7, 24.3, 30.5, 50.1, 52.9, 53.1, 83.5, 126.9, 128.3, 130.5, 131.3, 131.4, 153.7, 158.7, 165.2. Anal.Calcd.for C36H38Cl2N2O10: C, 59.26; H, 5.25; N, 3.84%. found: C, 59.33; H, 5.31; N, 3.76%.

2',3'-Dichloro-bis(diethyl-5-(cyclohexzylimino)-4'H,5H)dispiro[furan-2,1'-naphthalene]-3,3',4,4' tetra-carboxylate (4d):

Yield:93%; White powder; M.p.: 242-244 ºC. IR (KBr): = 2929, 2850, 1745, 1730, 1687 cm-1. MS (EI, 70eV) m/z: 784 (M+). 1H NMR (300 MHz, CDCl3): δ = 1.02-1.06 (m, 6H, 2CH3), 1.19-1.21(m, 6H, 2CH3), 1.39-1.82(m, 20H, 2Cy), 3.55-3.58 (m, 2H, CHN) 4.05-4.11(m, 4H, 2CH2), 4.46-4.50 (m, 4H, 2CH2), 7.24-7.47 (m, 4H, H-Ar). 13C NMR (75.47 MHz, CDCl3): δ = 13.7, 14.0, 24.6, 24.7, 25.6, 32.9, 33.3, 56.7, 61.7, 62.6, 86.5, 126.7, 130.13, 131.75, 132.1, 139.0, 143.2, 153.9, 158.9, 161.3. Anal.Calcd.for C40H46Cl2N2O10: C, 61.15; H, 5.90; N, 3.57%. found: C, 61.09; H, 5.85; N, 3.51%.

2',3'-Dichloro-bis(dimethyl-5-(2,6dimethylphenylimino)-4'H,5H)dispiro[furan-2,1'-naphthalene]-3,3',4,4'-tetra-carboxylate (4e):

Yield:88%, yellow powder;M.p.: 293-295 ºC.IR (KBr): = 2944, 1757, 1734, 1700, 1688.MS (EI, 70eV) m/z: 772 (M+). 1H NMR (300 MHz, CDCl3): δ =2.14 (s, 12H, 4CH3), 3.09 (s, 6H, 2CH3), 4.05 (s, 6H, 2CH3), 6.83-7.49 (m, 10H, H-Ar). 13C NMR (75 MHz,CDCl3): δ =18.1, 52.4, 53.6, 87.3, 123.8, 126.5, 127.1, 127.5, 130.6, 130.9, 131.6, 137.9, 143.5, 144.7, 153.9, 185.9, 161.2. Anal. Calcd. for C40H34Cl2N2O10: C, 62.10; H, 4.43; Cl, 9.17; N, 3.62%; Found: C, 62.02.18; H, 4.35; N, 3.57%.

Due to very low solubility of the products 4f, we cannot report the 13C NMR data for this product.

2',3'-Dichloro-bis(diethyl-5-(2,6dimethylphenylimino)-4'H,5H)dispiro[furan-2,1'-naphthalene]-3,3',4,4'-tetra-carboxylate (4f)

Yield:85%, yellow powder; M.p.: 243-245 ºC.IR (KBr): 2982,1750, 1728, 1694.MS (EI, 70eV) m/z: 828 (M+).1H NMR (300 MHz, CDCl3): δ = 0.33-0.38 (t, 6H,2CH3), 1.42-2.19 (m, 6H,2CH3), 3.52-3.57 (t, 4H, 2CH2), 4.49-4.56 (q, 4H, 2CH2 ), 6.79-7.50 (m, 10H, H-Ar).Anal. Calcd. for C44H42Cl2N2O10: C, 63.69; H, 5.10; N, 3.38%. Found: C, 63.61; H, 5.02; N, 3.29%.

2',3'-Dichloro-bis(dimethyl-5-(2,4,4-trimethylpentan-2-ylimino)-4'H,5H)dispiro [furan-2,1'-naphthalene]-3,3',4,4'-tetra-carboxylate (4g):

Yield:92%; White powder; M.p.: 213-215 ºC. IR (KBr): = 2958, 2895, 1757, 1729, 1687 cm-1. MS (EI, 70eV) m/z: 788 (M+). 1H NMR (300 MHz, CDCl3): δ = 1.01 (s, 18H, 2CH3), 1.32 (s, 6H, 2CH3), 1.36 (s, 6H, 2CH3), 1.60 (s, 2H, CH2), 3.61(6H, s, 2CH3), 3.96 (s, 6H, 2CH3), 7.23-7.45 (m, 4H, H-Ar). 13C NMR (75.47 MHz, CDCl3): δ= 29.30, 29.39, 31.64, 31.92, 52.60, 53.01, 55.48, 58.80, 86.86, 126.60, 129.99, 131.70, 131.95, 140.84, 141.54, 150.60, 159.53, 162.08. Anal.Calcd.for C40H50Cl2N2O10: C, 60.83; H, 6.38; N, 3.55%. found: C, 60.73; H, 6.44; N, 3.48%.

2',3'-dichloro-bis(diethyl-5-(2,4,4-trimethylpentan-2-ylimino)-4'H,5H)dispiro [furan-2,1'-naphthalene]-3,3',4,4'-tetra-carboxylate (4h):

Yield:91%; Yellow powder; M.p.: 181-183 ºC. IR (KBr): =2957, 2893, 1750, 1729, 1688cm-1. MS (EI, 70eV) m/z: 844 (M+). 1H NMR (300 MHz, CDCl3): δ = 1.00 (s, 18H, 6CH3), 1.04 (s, 6H, 2CH3), 1.31-1.42 (m,9H,3CH3), 1.60 (m, 4H, 2CH2), 4.05-4.11 (m, 4H, 2CH2), 4.38-4.45 (q, 4H, 2CH2), 7.24-7.44 (m, 4H, H-Ar). 13C NMR (75.47 MHz, CDCl3): δ = 13.8, 14.1, 29.3, 29.4, 31.7, 31.9, 55.3, 58.6, 61.5, 62.3, 86.9, 126.6, 129.8, 132.0, 132.1, 140.6, 141.5, 150.7, 159.0, 161.8. Anal.Calcd.for C44H58Cl2N2O10: C, 62.48; H, 6.91; N, 3.31%. found: C, 62.40; H, 6.87; N, 3.14%.

(Z)-Di-tert-butyl 2',3'-dichloro-5-(cyclohexylimino)-4'-oxo-4'H,5H-spiro[furan-2,1'-naphthalene]-3,4-dicarboxylate (6):

Yield:90%, white powder;M.p.: 160-163 ºC.. IR (KBr): = 3050, 2931, 2850, 1739, 1680.MS (EI, 70eV) m/z: 561 (M+). 1H NMR (300 MHz, CDCl3): δ =1.17-1.74 (m, 28H, Cy and 2C(Me)3), 3.59-3.65 (m, 1H, CHN), 7.27-8.25 (m, 4H, H-Ar). 13C NMR (75 MHz, CDCl3): δ =24.3,24.4, 15.7, 27.6, 27.7, 28.1, 33.1, 33.3, 56.3, 83.9, 84.3, 85.7,126.6, 127.8, 129.1, 130.1, 134.2, 137.5, 139.3, 142.7, 147.1, 153.3, 157.9, 160.1, 175.8. Anal. Calcd for C29H33Cl2NO6: C, 61.92; H, 5.91; N, 2.49%; Found: C, 61.89; H, 5.84; N, 2.42%.

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