Table 1.
Summary of solution and HEBM reactions (shaded lines are the solution reactions).
| No | Compound | Reagent 1 | NaOH/Reagent/CD (mole:mole:mole) | Reaction Time (h) | Yield (%) | DS | Residual Reagent 2 (%) |
|---|---|---|---|---|---|---|---|
| 1 | 2 | ClAcONa 3 | 6:5:1 | 3 | 89 | 4.3–4.5 | <2.5 |
| 2 | 2’ | ClAcONa | 6:5:1 | 1.5 | 96 | 4.3–4.6 | <2.5 |
| 3 | 2’ | ClAcONa | 6:5:1 | 2.5 | 98 | 4.4–4.6 | <0.5 |
| 4 | 2’ | ClAcONa 4 | 6:5:1 | 2.5 | 77 | 4.4–4.7 | <1.0 |
| 5 | 3’ | BuOAcr | 6:5:1 | 1.5 | 50 | 3.0–3.3 | ≈1.0 |
| 6 | 3’ | BuOAcr 4 | 6:5:1 | 2.5 | 30 | 2.8–3.2 | <1.0 |
| 7 | 3” | AcrONa | 6:5:1 | 3.5 | 52 | 2.8–3.1 | <11 |
| 8 | 3 | AcrAm 3 | 6:5:1 | 24 + 8 | 56 | 3.0–3.4 | <0.05 |
| 9 | 5 | AcrAm | 6:5:1 | 5.5 | 73 | 3.8–4.3 | <0.9 |
| 10 | 5 | AcrAm | 6:5:1 | 3.5 | 83 | 3.3–3.5 | <0.5 |
| 11 | 4 | BS 3 | 9.3:8.6:1 | 8 | 66 | 6.2–6.5 | <0.2 5 |
| 12 | 4’ | BS | 9:8:1 | 1.5 | 56 | 3.1–3.3 | ≈17 5 |
| 13 | 4’ | BS | 9:8:1 | 2.5 | 57 | 5.2–5.8 | ≈9.5 5 |
| 14 | 4’ | BS | 16:8:1 | 2.5 | 67 | 6.2–6.6 | <2 5 |
| 15 | 4’ | BS 4 | 16:8:1 | 2.5 | 72 | 7.5–7.8 | <0.6 5 |
| 16 | 4’ | BS 6 | 16:8:1 | 3 (1.5 + 1.5) | 71 | 4.4–4.9 | ≈9 5 |
| 17 | 4’ | BS | 16:8:1 | 3.5 | 79 | 6.9–7.5 | ≈0.6 5 |
1 ClAcONa: Sodium chloroacetate, BuOAcr: n-butyl acrylate, AcrONa: sodium acrylate, AcrAm: acrylamide, BS: 1,4-butanesultone; 2 or reagent derived by-product, calculated from 1H-NMR; 3 solution reaction; 4 from dried βCD (air dry βCD contains ≈14% water which was removed at 95–105 °C under reduced pressure using P2O5 and KOH); 5 residual 1,4-butanesultone; 6 BS was added in two equal portions.