反应详情

温度

78 °C

tert-Butyl phenyl carbonate (25.60 mL, 138.0 mmoles) was added to a stirred solution of 1,6-diaminohexane (15.30 g, 131.7 mmoles) in absolute EtOH (150 mL) in a 250 mL RB flask. The apparatus was fitted with a condenser and heated to 78° C. overnight under a blanket of nitrogen and then allowed to cool to room temperature. The solvent was stripped off the reaction mixture in vacuo (rotary evaporator) yielding a pale pink oily residue. CH2Cl2 (200 mL) was added to the residue and the resultant solution extracted with 3×200 mL portions of de-ionised water. For each extraction the pH of the aqueous phase was monitored and adjusted with HCl (aq, 2M) such that the pH of the aqueous layer was 3<pH<7 [only required for 1st extraction, needing ca. 60-70 mL HCl (aq, 2M)]. The aqueous phases were collected in a Erlenmeyer flask containing aqueous NaOH (aq, 100 mL, 3M). Ensuring that the pH of the collected aqueous extracts was ≧14 the resulting aqueous phase was extracted with CH2Cl2 (3×150 mL). These organic phases were recombined, evaporated to a volume of ca. 200 mL and subjected to the above pH modulated purification protocol for a second time by first extracting with water [3×200 mL, 3<pH<7 modulation with HCl (aq, 2M), again only required for 1st extract needing ca. 45-55 mL HCl (aq, 2M)], basicifying these aqueous extracts with NaOH (100 mL, 3M) and extracting with CH2Cl2 (3×150 mL). The CH2Cl2 extracts were combined, reduced in volume to 200 mL and then dried over anhydrous MgSO4, filtered, and stripped to dryness on a rotary evaporator for a period of 20 minutes to yield 6-(tert-butoxycarbonylamino)hexylamine as a peach oil. This peach oil was then subjected to a short path distillation using a Kugelrohr apparatus with an oven temperature of 180° C. and at a vacuum pressure of 0.160 torr, the receiver bulb was cooled by means of a dry-ice/acetone bath. Yield: 13.1 g (46%, colourless oil). 1H NMR (CDCl3) δ 1.14 (s, 2H, —NH2), 1.26-1.37 (m, 4H, —CH2—), 1.37-1.52 (s+m, 9H+4H, t-Bu+—CH2—), 2.67 (t, 2H, >NCH2—), 3.09 (q, 2H, —C(═O)NCH2—), 4.60 (bs, 1H, —C(═O)NH—).

1. customThe apparatus was fitted with a condenser
2. temperatureto cool to room temperature
3. customin vacuo (rotary evaporator)
4. customyielding a pale pink oily residue
5. extractionthe resultant solution extracted with 3×200 mL portions of de-ionised water
6. extractionFor each extraction the pH of the aqueous phase
7. extractiononly required for 1st extraction
8. customThe aqueous phases were collected in a Erlenmeyer flask
9. additioncontaining aqueous NaOH (aq, 100 mL, 3M)
10. extractionwas extracted with CH2Cl2 (3×150 mL)
11. customevaporated to a volume of ca. 200 mL
12. custompurification protocol for a second time
13. extractionby first extracting with water [3×200 mL, 3<pH<7 modulation with HCl (aq, 2M)
14. extractionfor 1st extract
15. extractionextracting with CH2Cl2 (3×150 mL)
16. dry with materialdried over anhydrous MgSO4
17. filtrationfiltered
18. customstripped to dryness on a rotary evaporator for a period of 20 minutes