tert-Butyl (3-aminopropyl)carbamate

Colorless to light yellow liquid

General procedure: To a cooled (0°C) suspension of 1, 6-diaminohexane (20.0g, 172mmol) in 50mL DCM was added a solution of BocTo a solution of 1, 3-DIAMINOPROPANE (100G, 1. 34MOL) in dry THF (1L) at 0°C was added BOC-ANHYDRIDE (98G, 0. 45mol). The reaction mixture was stirred at room temperature for 24h under N2. The reaction mixture was concentrated under reduced pressure. The residue was taken up in ethylacetate (2L) and was washed with brine (3X250ML) then dried and concentrated. The crude product was purified by chromatography (chloroform/methanol and methanol) to give TERT-BUTYL-3-AMINOPROPYL carbamate (65g, 82percent). TLC, CHLOROFORM/METHANOL, 9.5 : 0.5, RF=0. 2General procedure: Di-tert-butyl dicarbonate (3.63g, 0.017mol, dissolved in 10mL methanol) was added into a solution of diamine 1a (3.0g, 0.05mol) in triethylamine and methanol (10percent TEA in MeOH, 110mL), and the obtained solution was stirred at room temperature overnight. The methanol and TEA were removed in vacuo to yield an oily residue that was dissolved in dichloromethane (100mL) and washed with a solution of 10percent aq sodium carbonate (2×100mL). The organic layer was dried over anhydrous NaGeneral procedure: The appropriate diamine (10 eq) was dissolved in DCM and a solution of BocAsolution of tert-butyl dicarbonate (9.8 g, 45 mmol) in CHCl3 (300 mL)was added dropwise to a solution of 1, 3-propanediamine 6 (10 g, 135 mmol) in chloroform (30 mL) over 8 h, and the reaction mixturewas then stirred at room temperature for 15 h. The reaction mixturewas washed with saturated sodium bicarbonate solution (4 × 100 mL)and water (3 × 100 mL) and the organic phase was dried (MgSO4)and concentrated in vacuo to afforded amine 7: Colourless oil; yield5.41 g, 69percent; IR (νmax, cm–1) film: 3357 (w), 2975 (w), 1689 (s), 1517(s), 1250 (s); 1H NMR (300 MHz, CDCl3) δ 5.15 (1H, br. s, NHBoc), 3.04 (2H, m, CH2NHBoc), 2.62 (2H, t, J = 7 Hz, CH2NH2), 1.47 (2H, quint, J = 7 Hz, CH2CH2CH2), 1.31 (9H, s, 3 × CH3) 1.28 (2H, br. s, NH2); 13C NMR (75 MHz, CDCl3) δ 155.4 (s), 77.8 (s), 38.6 (t), 37.3(t), 32.5 (t), 26.9 (q); LRMS (ES) m/z (percent) 175 [M + H]+ (100), 215 [M+ CH3CN]+ (25). The data coincided with those reported in literature.6To a stirred and cooled solution (0°C) of 1, 3-diaminopropane (3.64mL, 43.5mmol) in CHClCompound 15 was synthesized in the following manner. Under argon, a solution of BocTo a solution of 1, 3-diaminopropane (28 mL, 335 mmol) in CHIntermediate 314the compound 1 - propylene diamine (30 g, 405 mmol, 1 eq) is dissolved in 150 ml dichloromethane in, ice bath stirring; the 2 - tert-butyl dicarbonate (16.1 g, 73 mmol, 0.18 eq) dissolved and diluted in 50 ml dichloromethane in; the mixture is slowly poured into a flask, stir at room temperature 3 hours; after the reaction is complete (TLC) thin layer chromatography detection, for 50 ml dichloromethane diluted and washed with water several times, then saturated NaCl solution for washing, after the anhydrous Na4.1.2.1 A triphenylphosphine (4.8 g; 18.3 mmol) solution in THF (15 mL) is added dropwise to a stirred solution of the above azide in THF (30 mL)/ H2O (0.3 mL; 18.3 mmol); the stirring is continued for 24 hrs at r. t.. After removal of the solvents to dryness in vacuum, the residue is taken up with a few of EtOH to separate a white precipitate of triphenylphosphine oxide by stirring for 6 hrs at r. t. The final EtOH removal to dryness, at low pressure, gives 3.22 g (18 mmol) of 1-BOC-propane-1, 3-diamine as a pale yellow oil. Intermediate 6: [4-(3-AMINOPROPYL ' MORPHOLINE-3N5-DIONE. H] Stepl : Tert-Butyl-3-aminopropyl carbamate To a stirred solution of 1, 3-diaminopropane (100g, 1. [34MOL)] in dry THF [(1L)] at [0°C] was added Boc-anhydride (98g, 0. [45MOL)] and the resulting solution was stirred at rt for 24h under N2. The reaction mixture was concentrated under reduced pressure and the crude residue obtained was dissolved in EtOAc (2L). The organic layer was washed with brine [(3X250ML), ] dried with [MGS04] and concentrated to near dryness. The crude product was purified by column chromatography over silica gel (chloroform/methanol and methanol) to give 65g [OF TERT-BUTYL-3-AMINOPROPYL] carbamate (82percent).251.6 g (3.4 mol, 1.5 eq) of 1, 3-propanediamine was mixed with 200 mL of isopropyl ether, cooled in ice water to 10° C., and then diisopropyl ether of tert-butyl azidocarboxylate was added dropwise thereto, and the reaction was incubated for 3 hours after completion of the dropwise addition. TLC detected the end of the reaction. The reaction solution was washed successively with 200 mL of water and 100 mL of saturated brine, and the organic phase was dried to obtain a crude product of single Boc-protected 1, 3-propanediamine after being concentrated, and the resulting solution was distilled under reduced pressure to obtain a colorless transparent liquid. It is a single Boc-protected 1, 3-propanediamine, its yield is 306.2 g, the GC purity is 98.4percent, and the total yield of the two-step reaction is 77.5percent. FIG. 2 is a result of a nuclear magnetic test of the product prepared in this example.

suzuki reaction

Molecular Weight:174.24
XLogP3:0.3
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:5
Exact Mass:174.136827821
Monoisotopic Mass:174.136827821
Topological Polar Surface Area:64.4
Heavy Atom Count:12
Complexity:141
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes