R. M. Shaker et al. · 1-Thia-5-azaspiro[5.5]undec-2-ene
491
(m, 4H, 2CH2), 2.91 (q, 2H, SCH2, J = 7.2 Hz), 7.36 – recrystallized from ethanol. Colorless powder, yield: 77 %,
7.55 (m, 10H, ArH), 8.51 (s, 1H, NH, D2O-exchangeable). – m. p. 251 – 252 ◦C. – IR (film): ν = 3202, 3059, 2212, 1671,
MS (EI, 70 eV): m/z (%) = 428 (36.46) [M]+. – Anal. for 1633, 1585 cm−1. – 1H NMR (300 MHz, [D6]DMSO): δ =
C25H24N4OS (428.55): calcd. C 70.07, H 5.64, N 13.07, 1.21 (t, 3H, CH3, J = 7.2 Hz), 1.88 – 2.23 (m, 8H, 4CH2),
S 7.48; found C 69.96, H 5.72, N 12.95, S 7.41.
3.36 (s, 2H, SCH2), 4.12 (q, 2H, OCH2, J = 7.2 Hz), 7.37 –
7.51 (m, 10H, ArH), 8.55 (s, 1H, NH). – 13C NMR (75 MHz,
[D6]DMSO): δ = 13.89 (CH3), 31.36 (CH2), 31.82 (CH2),
34.84 (2CH2), 42.67 (SCH2), 61.50 (C-CN), 73.73 (C-6),
86.87 (C-3), 116.30 (CN), 121.60 (CN), 125.52, 128.12,
128.90, 129.42, 129.57, 138.35, 139.45 (C-Ar), 160.66 (CO),
162.27 (CO), 167.42 (C-2) . – MS (EI, 70 eV): m/z (%) = 486
(20.33) [M]+. – Anal. for C27H26N4O3S (486.59): calcd.
C 66.65, H 5.39, N 11.51, S 6.59; found C 66.47, H 5.51,
N 11.42, S 6.53.
2-Benzylthio-3,9-dicyano-1,9-diphenyl-4-oxo-1,5-diaza-
spiro[5.5]undec-2-ene (13)
A mixture of compound 7 (4.00 g, 0.01 mol), benzyl
chloride (1.68 g, 0.011 mol), and triethylamine (2.1 mL,
0.015 mol) in ethanol (20 mL) was refluxed, and a color-
less precipitate was formed after half an hour. The reaction
was continued for 2 h, and the resulting precipitate was fil-
tered off, dried, and recrystallized from DMF / EtOH. Color-
less crystals yield: 79 %, m. p. 261 – 262 ◦C. – IR (film): ν =
3162, 3053, 2209, 1651, 1530 cm−1. – 1H NMR (300 MHz,
[D6]DMSO): δ = 1.72 – 1.81 (m, 2H, CH2), 1.97 – 2.24 (m,
6H, 3CH2), 4.19 (s, 2H, SCH2), 7.08 – 7.52 (m, 15H, ArH),
8.41 (s, 1H, NH, D2O-exchangeable). – MS (EI, 70 eV): m/z
(%) = 490 (5.6) [M]+. – Anal. for C30H26N4OS (490.62):
calcd. C 73.44, H 5.34, N 11.42, S 6.54; found C 73.36,
H 5.42, N 11.32, S 6.48.
5ꢀ-Amino-4,6ꢀ-dicyano-1ꢀ,4-diphenyl-4ꢀ-oxo-3ꢀ,4ꢀ-dihydro-
1ꢀH-spiro[cyclohexane-1,2ꢀ-thieno[2,3-d]pyrimidine] (18)
To a stirred 0.75 N aqueous KOH solution (20 mL),
compound 7 (0.40 g, 10 mmol) and bromoacetonitrile (16)
(0.24 g, 20 mmol) were added successively. The result-
ing precipitate was filtered off, washed with water, dried
and recrystallized from ethanol. Grey powder, yield: 80 %,
m. p. 330 – 332 ◦C. – IR (film): ν = 3429 – 3310, 3202, 2185,
1642, 1514 cm−1. – 1H NMR (300 MHz, [D6]DMSO): δ =
1.85 – 2.36 (m, 8H, 4CH2), 6.82 (s, 2H, NH2), 7.34 – 7.59 (m,
10H, ArH), 8.50 (s, 1H, NH). – MS (EI, 70 eV): m/z (%) =
439 (46) [M]+. – Anal. for C25H21N5OS (439.53): calcd.
C 68.32, H 4.82, N 15.93, S 7.30; found C 68.24, H 4.93,
N 15.84, S 7.18.
Ethyl 2-(3,9-dicyano-4-oxo-1,9-diphenyl-1,5-diazaspiro-
[5.5]undec-2-en-2-ylthio)acetate (15)
To a stirred 0.75 N aqueous KOH solution (20 mL), com-
pound 7 (0.40 g, 10 mmol) and ethyl bromoacetate (14)
(0.33 g, 20 mmol) were added successively. The resulting
precipitate was filtered off, washed with water, dried and
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Unauthenticated
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