Structure of 3518-88-5
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CAS No. : | 3518-88-5 |
Formula : | C10H19NO4 |
M.W : | 217.26 |
SMILES Code : | O=C(OCC)CCNCCC(OCC)=O |
MDL No. : | MFCD14705114 |
Boiling Point : | No data available |
InChI Key : | ONEIYJQBXMVMKU-UHFFFAOYSA-N |
Pubchem ID : | 352310 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319 |
Precautionary Statements: | P264-P280-P302+P352-P337+P313-P305+P351+P338-P362+P364-P332+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 |
---|---|---|
96% | With palladium 10% on activated carbon; ammonium formate; In ethanol; for 2.0h;Reflux; | Diethyl 3,3'-(benzylazanediyl)dipropanoate (16) was made according to the literature method14 in a yield of 91.2%. 1H NMR (400 MHz, CDCl3) δ 1.23 (t, J = 7.1 Hz, 6H), 2.45 (t, J = 7.1 Hz, 4H), 2.81 (t, J = 7.1 Hz, 4H), 3.60 (s, 2H), 4.10 (q, J = 7.1 Hz, 4H), 7.22-7.29 (m, 5H). MS (APCI+): m/z 308.2 (M+1). Calcd for C17H25NO4: M+ 307.2.A mixture of 16 (4.88 g, 15.9 mmol), HCO2NH4 (10.0 g, 159 mmol) and 10% Pd-C catalyst (2.44 g) in EtOH (ca. 350 mL) was heated at reflux and stirred for 2 h before all the volatiles were removed under reduced pressure. The residue was dissolved in CH2Cl2, filtered through Celite, and evaporated to give diethyl 3,3'-azanediyldipropanoate (17) as a pale yellow liquid (3.30 g, 96%), which had identical 1H NMR characteristics to those reported in the literature.13 MS (APCI+): m/z 218.1 (M+1). Calcd for C10H19NO4: M+ 217.1.Oxalyl chloride (3.92 mL, 46.33 mmol) was added dropwise to a stirred solution of 6-bromohexanoic acid (4.39 g, 22.50 mmol) and DMF (ca. 0.2 mL) in dry CH2Cl2 (50 mL), and the reaction was then stirred overnight. All the volatiles were removed under reduced pressure, and the resulting oil was pumped under high vacuum. The crude 6-bromohexanoyl chloride was dissolved in CH2Cl2 (40 mL) and added portionwise by syringe into a solution of 17 (3.20 g, 14.73 mmol) and NEt3 (10.45 ml, 75.00 mmol) in CH2Cl2 (25 mL). LC-MS was used to monitor the reaction. After 30 mL of the acid chloride solution was added, LC-MS showed most of the diethyl 3,3'-azanediyldipropanoate had reacted. The mixture was stirred for a further 2 h before being washed with aqueous NaHCO3, brine, dried over anhydrous Na2SO4 and filtered. Solvent was removed and the crude product was subjected to flash chromatography (4 × 20 cm silica gel; EtOAc/petroleum ether; 1:3 to 1:1, gradient elution) to give diethyl 3,3'-(6-bromohexanoylazanediyl)dipropanoate (18) as a colorless oil (4.73 g, 81%): 1H NMR (400 MHz, CDCl3) δ 1.24-1.29 (m, 6H), 1.44-1.52 (m, 2H), 1.62-1.70 (m, 2H), 1.85-1.92 (m, 2H), 2.35 (t, J = 7.4 Hz, 2H), 2.55-2.61 (m, 4H), 3.42 (t, J = 6.8 Hz, 2H), 3.58 (t, J = 7.0 Hz, 2H), 3.64 (t, J = 7.3 Hz, 2H), 4.10-4.18 (m, 4H). MS (APCI+): m/z 394.3/396.3 (1:1, M+1). Calcd for C16H2879/81BrNO5: M+ 393.1/395.1.A mixture of 18 (830 mg, 2.11 mmol), dibenzyl 1,4,7,10-tetraazacyclododecane-1,7-dicarboxylate (19)16 (440 mg, 1.00 mmol), and K2CO3 (552 mg, 4.00 mmol) in DMF (10 mL) was stirred at room temperature for 7 h and then at 60 C for 15 h. The mixture was poured into water and extracted with Et2O (×4). The extracts were combined and washed with water, brine, dried over Na2SO4 and filtered. The filtrate was evaporated and the residue obtained was subjected to flash chromatography (silica gel: NEt3/MeOH/CH2Cl2; 0.25:2.5:100 to 0.5:5:100, gradient elution) to give dibenzyl 4,10-bis(6-(bis(3-ethoxy-3-oxopropyl)amino)-6-oxohexyl)-1,4,7,10-tetraazacyclododecane-1,7-dicarboxylate (20) (506 mg, 47%) as a colorless oil: 1H NMR (400 MHz, CDCl3) δ 1.23-1.28 (m, 16H), 1.41 (br, 4H), 1.58 (br, 4H), 2.29-2.42 (br, 8H), 2.54-2.65 (m, 16H), 3.42 (br, 8H), 3.55-3.64 (m, 8H), 4.10-4.17 (m, 8H), 5.12 (s, 4H), 7.27-7.35 (m, 10H). MS (APCI+): m/z 1068.0 (M+1). Calcd for C56H86N6O14: M+ 1066.6. Further elution with NEt3/MeOH/CH2Cl2 (1:10:100) gave another colorless oil (202 mg, 27%), which appeared by NMR and MS to be the mono-alkylated product: 1H NMR (400 MHz, CDCl3) δ 1.23-1.60 (m, 16H), 2.25-2.76 (m, 12H), 3.40-3.65 (m, 12H), 4.10-4.16 (m, 4H), 45.12-5.17 (m, 4H), 7.28-7.34 (m, 10H), 11.0 (br, 1H). MS (APCI+): m/z 754.3 (M+1). Calcd for C40H59N5O9: M+ 753.4.A mixture of 20 (155 mg, 0.14 mmol) and 5% Pd-C (80 mg) in EtOH (5 mL) was hydrogenated under 60 psi of hydrogen gas for 15 h. Solvent was removed and the resulting residue was taken up in CH2Cl2 and the catalyst was filtered off. Removal of the solvent gave 1,7-bis(6-(bis(3-ethoxy-3-oxopropyl)amino)-6-oxohexyl)-1,4,7,10-tetraazacyclododecane (21) (100 mg, 86%) as a colorless viscous oil: 1H NMR (400 MHz, CDCl3) δ 1.24-1.36 (m, 16H), 1.45-1.53 (m, 4H), 1.60-1.67 (m, 4H), 2.35 (t, J = 7.4 Hz, 4H), 2.52-2.62 (m, 12H), 2.75 (br, 8H), 2.86 (br, 8H), 3.57 (t, J = 7.0 Hz, 4H), 3.65 (t, J = 7.2 Hz, 4H), 4.10-4.18 (m, 8H). 13C NMR (100 MHz, CDCl3) single peaks at δ 14.01, 24.80, 26.66, 26.75, 32.67, 33.87, 41.99, 44.00, 47.15, 51.31, 56.24, 60.37, 60.74, 170.80, 171.77, 172.77. MS (APCI+): m/z 799.6 (M+1). Calcd for C40H74N6O10: M+ 798.5.A solution of 21 (100 mg, 0.12 mmol) and NaOH (1 mL, 1.0 mol L-1) in EtOH (5 mL) was stirred for 15 h. The mixture was neutralized with HCl (1 mL, 1.0 mol L-1) to pH 5-6. All volatiles were removed and the residue was extracted with EtOH and the solid (NaCl) was filtered off. Removal of solvent gave 3,3',3,3-(6,6'-(1,4,7,10-tetraazacyclododecane-1,7-diyl)bis(hexanoyl)bis(azanediyl))tetrapropanoic acid (H4L11) (90 mg, 100%) as a pale yellow solid: 1H NMR (400 MHz, D2O) δ 1.31-1.35 (m, 4H), 1.59-1.63 (m, 8H), 2.45 (t, J = 7.4 Hz, 4H), 2.61 (t... |
93.4% | With 5%-palladium/activated carbon; hydrogen; In ethanol; under 760.051 Torr; for 20.0h; | Example 4 Synthesis of Diethyl 3, 3'-iminodipropionate The Michael adduct of benzyl amine and ethyl acrylate of Example 3 (10 g, 32.5 mmol) in ethanol (50 mL) and Pd on charcoal (5% Pd/C, 100 mg) was stirred under hydrogen at atmospheric pressure for 20 hours. The catalyst was filtered off and the filtrate was made free of any volatiles by rotary evaporation under reduced pressure at 50 C. to yield diethyl iminodipropionate (6.6 g, 93.4%) as pale yellow viscous liquid. IR (cm-1): 1728, 2838, 2981 and 3330 1H NMR (CDCl3): δ 1.90 (6H, t, J=5.4 Hz), 2.82 (4H, t, J=6 Hz), 2.43 (4H, t, J=4.8 Hz), 4.0 (4H, q, J=5.4 Hz) |
Tags: 3518-88-5 synthesis path| 3518-88-5 SDS| 3518-88-5 COA| 3518-88-5 purity| 3518-88-5 application| 3518-88-5 NMR| 3518-88-5 COA| 3518-88-5 structure
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