A. R. Katritzky et al. / Tetrahedron: Asymmetry 21 (2010) 51–57
57
4.11. (1S,10S)-1,10-[(1-(p-Nitrobenzoyl)-1H-1,2,4-triazole-3,5-diyl)]-
bis(ethane-1,1-diyl)-bis(p-nitro- benzoate) 11
temperature, the residue was extracted with dichloromethane
(30 mL x 2) which was washed with water and evaporated in vacuo
at room temperature to give 160 (0.28 g, 90%). The product was
then recrystallized from a mixture of dichloromethane and hex-
anes by freezing to give white crystals (0.28 g, 90%): mp = 189–
A mixture of 4 (0.31 g, 2 mmol), p-nitrobenzoyl chloride (1.11 g,
6 mmol), and triethylamine (0.60 g, 6 mmol) in THF (10 mL) was
stirred at room temperature for 12 h and was filtered to remove tri-
ethylamine hydrochloride. The resulting solution was evaporated
under reduced pressure and the residue was purified by flash silica
gel chromatography (eluent: dichloromethane/hexanes = 1:1) to
give 11 (0.60 g, 50%). Crystallization from a mixture of dichloro-
methane/petroleum ether by freezing gave the product with mp =
57–60 °C. Further purification by column chromatography (eluent:
191 °C; ½a 2D5
ꢀ
¼ þ61:5 (c = 2, CH2Cl2); 1H NMR (CDCl3) d 3.78 (s,
3H), 5.75 (d, J = 6.9 Hz, 1H), 7.29 (d, J = 6.9 Hz, 1H), 7.35–7.48 (m,
5H), 7.97 (d, J = 8.9 Hz, 2H), 8.27 (d, J = 8.9 Hz, 2H); 13C (CDCl3) d
53.1, 57.0, 123.8, 127.3, 128.4, 128.9, 129.1, 135.9, 139.0, 149.7,
164.5, 171.2. Anal. Calcd for C16H14N2O5: C, 61.14; H, 4.49; N,
8.91. Found: C, 60.95; H, 4.43; N, 8.76.
dichloromethane) gave the product: mp 67–70 °C; ½a D25
ꢀ
¼ þ87:5 (c
4.16. Methyl (R)-(4-nitro-benzoylamino)phenylacetate 16
This enantiomer was prepared by the same procedure as 160
2, CH2Cl2). 1H NMR (CDCl3) d 1.79 (d, J = 6.7 Hz, 3H), 1.93 (d,
J = 6.6 Hz, 3H), 6.23 (q, J = 6.7 Hz, 1H), 6.63 (q, J = 6.6 Hz, 1H), 8.17–
8.31 (m, 12H); 13C NMR (CDCl3) d 18.5, 18.8, 66.8, 67.4, 123.2,
123.5, 123.6, 130.8, 130.9, 132.7, 134.8, 135.0, 135.9, 150.7, 150.8,
161.3, 163.2, 163.9, 164.1, 164.5. Anal. Calcd for C27H20N6O11: C,
53.65; H, 3.33; N, 13.90. Found: C, 53.74; H, 3.23; N, 13.52.
(0.29 g, 94%); mp 190–191 °C; ½a D25
ꢀ
¼ ꢁ62:7 (c 2, CH2Cl2); 1H NMR
(CDCl3) d 3.79 (s, 3H), 5.75 (d, J = 7.0 Hz, 1H), 7.27 (d, J = 7.0 Hz,
1H), 7.35–7.48 (m, 5H), 7.97 (d, J = 8.8 Hz, 2H,), 8.27 (d, J = 8.8 Hz,
2H); 13C NMR(CDCl3) d 53.1, 57.0, 123.8, 127.3, 128.4, 128.9, 129.2,
135.9, 139.0, 149.8, 164.5, 171.2. Anal. Calcd for C16H14N2O5: C,
61.14; H, 4.49; N, 8.91. Found: C, 60.98; H, 4.50; N, 8.80.
4.12. (1S,10S)-1,10-(1-Acetyl-1H-1,2,4-triazole-3,5-diyl)-bis(ethane-
1,1-diyl)diacetate 12
Acknowledgment
A solution of acetic anhydride (22 g, 21 mmol) and 4 (1.60 g,
10 mmol) was mixed at room temperature, then potassium carbon-
ate (0.14 g, 1 mmol) in water (2 mL) was added. The mixture was
kept under stirring for 2 h at the same condition, was evaporated un-
til dry, then dissolved with dichloromethane (30 mL); washed with
water (20 mL) twice, then with brine (20 mL) twice. The organic
layer was further dried over MgSO4. The solvent was removed under
reduced pressure, and the residue was dried in vacuo to yield 12
We thank Dr. Tamari Narindoshvili for her useful suggestions.
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ꢀ
¼ ꢁ131:9 (c 2, CH2Cl2). 1H NMR
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1,2,4-triazol-3-yl]-ethyl ester 13
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The second product isolated during column separation of 11 was
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¼ þ36:6 (c 2,
ꢀ
CH2Cl2); 1H NMR (CDCl3) d 1.87 (d, J = 6.7 Hz, 6H), 6.28 (q, J = 6.7 Hz,
2H), 8.17–8.30 (m, 9H); 13C NMR (CDCl3) d 18.8, 66.8, 123.6, 131.0,
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4.14. (1S,10S)-1,10-(1H-1,2,4-Triazole-3,5-diyl)-bis-(ethane-1,1-
diyl) diacetate 14
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(2.29 g, 95%): colorless oil; ½a D25
ꢀ
¼ ꢁ156 (c 2, CH2Cl2); 1H NMR
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2H); 13C NMR (CDCl3) d 19.9, 21.0, 65.4, 159.6, 170.6. Anal. Calcd
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4.15. Methyl (S)-(4-nitro-benzoylamino)phenylacetate 160
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(0.20 g, 1 mmol), p-nitrobenzoyl chloride (0.18 g, 1 mmol), and tri-
ethylamine (0.20 g, 2 mmol) in THF (10 mL) was stirred at room
temperature for 12 h. THF was removed under vacuum at room