Structure of 94391-71-6
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CAS No. : | 94391-71-6 |
Formula : | C6H12N2O |
M.W : | 128.17 |
SMILES Code : | O=C([C@H]1N(C)CCC1)N |
MDL No. : | MFCD19206880 |
InChI Key : | IGERQMDMYFFQLC-YFKPBYRVSA-N |
Pubchem ID : | 14245857 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319 |
Precautionary Statements: | P264-P280-P302+P352+P332+P313+P362+P364-P305+P351+P338+P337+P313 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
13% | With potassium phosphate; palladium diacetate; In tetrahydrofuran; at 70℃; for 16.0h; | Synthesis of enamide 7 To a solution of compound 24 (271 mg, 0.63 mmol) in anhydrous THF (2 mL) were added prolinamide 25 26 (40.5 mg, 0.32 mmol), Pd(OAc)2 (7.1 mg, 0.03 mmol) and K3PO4 (202 mg, 0.95 mmol). Resultant reaction solution was stirred at 70 C for 16 h. After that reaction solution was cooled up to room temperature and filtered through a small silica gel pad and eluted with CH2Cl2. Filtrate was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (20-60% EtOAc/hexane) to give product 7 (20.6 mg, 13%) was obtained as a yellowish liquid. Rf (60% EtOAc/hexane) 0.4; -6.3 (c 0.12, CHCl3); νmax (neat) 3326, 2922, 2852, 1695, 1644, 1464, 1389, 1262, 1064, 733 cm-1; 1H NMR (500 MHz, CDCl3) δ 9.40 (d, 1H, J=11.6 Hz), 7.04 (dd, 1H, J=9.6 Hz, 12.1 Hz), 6.89 (s, 1H), 5.81 (d, 1H, J=9.5 Hz), 3.89 (s, 3H), 3.05 (t, 1H, J=7.8 Hz), 3.00 (dd, 1H, J=5.5 Hz, 10.4 Hz), 2.38-2.35 (m, 1H), 2.34 (s, 3H), 2.28-2.22 (m, 1H), 1.91-1.84 (m, 1H), 1.83-1.77 (m, 1H), 1.73-1.63 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 172.6, 156.2, 137.1, 130.5, 123.1, 118.2, 110.4, 68.9, 56.82, 56.77, 42.3, 31.1, 24.6; HRMS (ESI): MH+, found 494.8914. C15H18Br3N2O2 requires 494.8918. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
15%; 40% | With potassium phosphate; palladium diacetate; In tetrahydrofuran; at 70 - 80℃; for 13.0h;Catalytic behavior; | Syntheses of enamides 8 and 4 To a solution of compound 28 (856 mg, 2.0 mmol) in anhydrous THF (10 mL) were added prolinamide 25 (128 mg, 1.0 mmol), Pd(OAc)2 (22.5 mg, 0.1 mmol) and K3PO4 (637 mg, 3.0 mmol). Resultant reaction solution was stirred at 70-80 C for 13 h. After that reaction solution was cooled up to room temperature and filtered through a small silica gel pad and eluted with CH2Cl2. Filtrate was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (20-60% EtOAc/hexane) to give Z-enamide 8 (75 mg, 15%) as a light yellow liquid and E-enamide 4 6 (197 mg, 40%) as a white solid. 4.11.1 Data for Z-enamide 8 (0037) Rf (60% EtOAc/hexane) 0.8; [α]22D[α]D22 -16.8 (c 0.95, CHCl3); νmax (neat) 3315, 3067, 2936, 2850, 1699, 1653, 1478, 1022, 928, 757cm-1; 1H NMR (500MHz, CDCl3) δ 8.87 (d, 1H, J=11.3Hz), 7.82 (s, 1H), 7.02 (dd, 1H, J=9.3Hz, 12.1Hz), 5.57 (d, 1H, J=9.5Hz), 3.88 (s, 3H), 2.99 (t, 1H, J=7.2Hz), 2.95 (dd, 1H, J=4.9Hz, 10.4Hz), 2.32-2.27 (m, 1H), 2.29 (s, 3H), 2.24-2.16 (m, 1H), 1.90-1.84 (m, 1H), 1.77-1.64 (m, 2H); 13C NMR (125MHz, CDCl3) δ 172.6, 154.3, 137.2, 135.6, 123.9, 121.0, 119.3, 117.3, 108.8, 68.7, 60.6, 56.7, 42.1, 31.2, 24.6; HRMS (ESI): MH+, found 494.8918. C15H18Br3N2O2 requires 494.8918. 4.11.2 Data for E-enamide 4 (0038) Mp 132-134C; Rf (60% EtOAc/hexane) 0.6; [α]22D[α]D22 -65.0 (c 1.0, CH2Cl2) [lit.6 [α]23D[α]D23 -9.8 (c 0.01, CH2Cl2)]; νmax (neat) 3268, 2971, 2842, 2779, 1669, 1641, 1476, 1346, 1211, 1043, 978, 890, 716cm-1; 1H NMR (500MHz, CDCl3) δ 9.23 (d, 1H, J=11.3Hz), 7.78 (s, 1H), 7.42 (dd, 1H, J=11.6Hz, 14.7Hz), 6.06 (d, 1H, J=15.0Hz), 3.87 (s, 3H), 3.20-3.17 (m, 1H), 3.02 (dd, 1H, J=5.2Hz, 10.4Hz), 2.45 (s, 3H), 2.43-2.40 (m, 1H), 2.32-2.24 (m, 1H), 1.97-1.91 (m, 1H), 1.85-1.79 (m, 2H); 13C NMR (125MHz, CDCl3) δ 172.7, 154.1, 137.5, 135.7, 129.7, 120.8, 118.7, 115.9, 110.4, 68.8, 60.6, 56.8, 42.2, 31.1, 24.6; HRMS (ESI): MH+, found 494.8927. C15H18Br3N2O2 requires 494.8918. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
16% | With potassium phosphate; palladium diacetate; In neat (no solvent); at 20℃; for 36.0h; | 4.14 Synthesis of (S)-1-methyl-N-vinylpyrrolidine-2-carboxamide 31 To a solution of prolinamide 25 26 (64 mg, 0.5 mmol) in vinyl acetate (1 mL) were added Pd(OAc)2 (11.3 mg, 0.05 mmol) and K3PO4 (106 mg, 0.5 mmol). Resultant reaction solution was stirred at room temperature for 36 h. After that all volatiles were removed under reduced pressure and the residue was purified by silica gel column chromatography (20-80% EtOAc/hexane) to give 31 (12.5 mg, 16%; 37% based on recovered starting material) as a colorless viscous liquid; Rf (30% EtOAc/hexane) 0.6; -89.1 (c 0.5, CHCl3); νmax (neat) 3307, 2940, 2805, 1730, 1666, 1639, 1494, 1371, 1238, 1045, 857 cm-1; 1H NMR (400 MHz, CDCl3) δ 9.22 and 9.09 (each br s, due to geometrical isomer, 1H), 6.98-6.84 (m, 1H), 5.42 and 5.16 (each q, due to geometrical isomer, 1H, J=6.5 Hz), 4.66 (dd, 1H, J=8.8 Hz, 15.9 Hz), 4.43 (t, 1H, J=7.7 Hz), 3.15-3.11 and 3.04-3.02 (each m, due to geometrical isomer, 1H), 2.97-2.91 and 2.77-2.72 (each m, due to geometrical isomer, 1H), 2.60 and 2.45 (each s, due to geometrical isomer, 3H), 2.11-2.07 (m, 2H), 2.04 and 2.01 (each s, due to geometrical isomer, 3H), 1.87-1.67 (m, 3H), 1.48 and 1.40 (each d, due to geometrical isomer, 3H, J=6.6 Hz); 13C NMR (125 MHz, CDCl3) δ 172.5, 171.9, 170.3 and 169.8 (due to geometrical isomer), 128.8 and 128.6 (due to geometrical isomer), 95.6 and 95.5 (due to geometrical isomer), 73.5, 72.7, 71.7 and 71.6 (due to geometrical isomer), 56.2 and 56.0 (due to geometrical isomer), 36.4, 35.6, 35.5 and 34.6 (due to geometrical isomer), 23.4, 23.2 and 21.5 (due to geometrical isomer), 17.3 and 16.3 (due to geometrical isomer); HRMS (APCI): MH+, found 155.1175. C8H15N2O requires 155.1184. |
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