Table 1.
No. | Compound | Purity | tRc (min) | MSd (M + H)+ | pIC50e | IC50f (nM) | Duration of actiong | ||
---|---|---|---|---|---|---|---|---|---|
HPLCa | CZEb | Calc. | Obs. | Avg. ± SEM | |||||
1 | [Ac-d-2Nal1,d-4Cpa2,d-3Pal3,4Aph(l-Hor)5,d-4Aph(Cbm)6,Ilys8,d-Ala10]GnRH (degarelix) | 96 | 98 | 23.8 | 1631.8 | 1631.9 | 9.24 ± 0.16 | 0.58 | Very long |
2 | [Ac-d-2Nal1,d--4Cpa2,d-3Pal3, 4Aph(Ac)5,d-4Aph(Ac)6,Ilys8,d-Ala10]GnRH (acyline) | 98 | 98 | 28.2 | 1532.7 | 1532.7 | 9.16 ± 0.06 | 0.69 | Long |
3 | [d-Dap(CO-NH-OH)3]degarelix | 97 | 98 | 21.7 | 1628.7 | 1628.7 | 8.46 ± 0.01 | 3.46 | Short |
4 | [d-Dab(CO-NH-OH)3]degarelix | 99 | 99 | 21.3 | 1642.8 | 1642.8 | 8.57 ± 0.12 | 2.68 | Short |
5 | [d-Dap(CO-NH-OCH3)3]degarelix | 95 | 99 | 23.3 | 1642.8 | 1642.7 | 8.50 ± 0.02 | 3.16 | Short |
6 | [d-Dab(CO-NH-OCH3)3]degarelix | 98 | 98 | 22.8 | 1656.8 | 1656.8 | 8.77 ± 0.05 | 1.69 | Short |
7 | [4Aph(CO-NH-OH)5]degarelix | 99 | 98 | 24.4 | 1550.7 | 1550.7 | 9.07 ± 0.19 | 0.86 | Short |
8 | [4Aph(CO-NH-OCH3)5]degarelix | 99 | 99 | 26.3 | 1564.7 | 1564.7 | 9.22 ± 0.03 | 0.60 | Long |
9 | [4Aph(CO-NH-(C2H4O)2-C2H5)5]degarelix | 98 | 98 | 29.1 | 1650.8 | 1650.8 | 8.50 ± 0.62 | 3.16 | Long* |
10 | [4Aph(CO-(C2H4O)3-C2H4-NH-CO-NH-OCH3)5]degarelix | 98 | 97 | 26.1 | 1767.9 | 1767.9 | 8.97 ± 0.13 | 1.06 | Short |
11 | des-Ac-[4Aph(CO-NH-OCH3)5]-CH3-(CH2)2-CO-degarelix | 98 | 97 | 30.1 | 1592.8 | 1592.7 | 8.83 ± 0.31 | 1.46 | Long* |
12 | des-Ac-[4Aph(CO-NH-OCH3)5]-CH3-(CH2)6-CO-degarelix | 97 | 98 | 40.4 | 1648.8 | 1648.6 | 8.38 ± 0.14 | 4.17 | Short |
13 | des-Ac-[4Aph(CO-NH-OCH3)5]-C2H5-(C2H4O)2-NH-CO-degarelix | 96 | 96 | 30.6 | 1681.8 | 1681.9 | 8.53 ± 0.47 | 2.98 | Long* |
14 | des-Ac-[4Aph(CO-NH-(C2H4O)2-C2H5)5]-C2H5-(C2H4O)2-NH-CO-degarelix | 95 | 95 | 33.3 | 1767.9 | 1767.9 | 8.95 ± 0.04 | 1.12 | Short |
15 | [d-4Aph(CO-NH-OH)6]degarelix | 97 | 99 | 23.7 | 1647.7 | 1647.7 | 9.09 ± 0.12 | 0.80 | Long* |
16 | [d-4Aph(CO-NH-OCH3)6]degarelix | 98 | 99 | 26.0 | 1661.8 | 1661.8 | 9.29 ± 0.12 | 0.51 | Long* |
17 | [d-4Aph(CO-NH-(C2H4O)2-C2H5)6]degarelix | 98 | 98 | 28.3 | 1747.8 | 1747.9 | 9.06 ± 0.11 | 0.88 | Short |
18 | des-Ac-[d-4Aph(CO-NH-OCH3)6]-CH3-(CH2)2-CO-degarelix | 98 | 98 | 29.7 | 1689.8 | 1689.9 | 8.67 ± 0.26 | 2.13 | Short |
19 | des-Ac-[d-4Aph(CO-NH-OCH3)6]-CH3-(CH2)6-CO-degarelix | 98 | 98 | 39.6 | 1745.9 | 1745.8 | 8.02 ± 0.18 | 9.47 | Short |
20 | des-Ac-[d-4Aph(CO-NH-OCH3)6]-C2H5-(C2H4O)2-NH-CO-degarelix | 95 | 99 | 29.9 | 1778.8 | 1778.7 | 8.79 ± 0.25 | 1.61 | Short |
21 | des-Ac-[d-4Aph(CO-NH-(C2H4O)2-C2H5)6]-C2H5-(C2H4O)2-NH-CO-degarelix | 95 | 99 | 32.1 | 1864.9 | 1864.9 | 8.34 ± 0.37 | 4.55 | ND |
22 | [4Aph(CO-NH-OCH3)5,d-4Aph(CO-NH-OCH3)6]degarelix | 95 | 96 | 28.5 | 1594.8 | 1594.8 | 9.04 ± 0.01 | 0.91 | Long* |
23 | [Nα-Me-4Aph(CO-NH-OCH3)5,d-4Aph(CO-NH-OCH3)6]degarelix | 99 | 98 | 28.9 | 1608.8 | 1608.8 | 9.15 ± 0.05 | 0.70 | Short |
24 | [4Aph(CO-NH-(C2H4O)2-C2H5)5,d-4Aph(CO-NH-(C2H4O)2-C2H5)6]degarelix | 96 | 99 | 33.5 | 1767.0 | 1767.1 | 8.69 ± 0.31 | 2.04 | Short |
25 | [4Aph(CO-NH-OCH3)5,d-4Aph(CO-(C2H4O)6-C2H4-NH-CO-NH-OCH3)6]degarelix | 98 | 98 | 28.5 | 1929.9 | 1929.8 | 8.78 ± 0.24 | 1.67 | Short |
26 | des-Ac-[4Aph(CO-NH-OCH3)5,d-4Aph(CO-NH-OCH3)6]-CH3-(CH2)2-CO-degarelix | 99 | 99 | 32.3 | 1622.8 | 1622.9 | 8.86 ± 0.35 | 1.37 | Short |
27 | des-Ac-[4Aph(CO-NH-OCH3)5,d-4Aph(CO-NH-OCH3)6]-CH3-(CH2)6-CO-degarelix | 99 | 99 | 42.5 | 1678.8 | 1678.9 | 8.30 ± 0.34 | 4.99 | Inactive |
28 | des-Ac-[4Aph(CO-NH-(C2H4O)2-C2H5)5,d-4Aph(CO-NH-(C2H4O)2-C2H5)6]-C2H5-(C2H4O)2-NH-CO-degarelix | 95 | 97 | 37.6 | 1883.9 | 1883.9 | 8.59 ± 0.22 | 2.55 | Short |
29 | [d-Gln3, 4Aph(CO-NH-OCH3)5,d-4Aph(CO-NH-OCH3)6]degarelix | 99 | 99 | 27.6 | 1574.7 | 1574.7 | 8.53 ± 0.24 | 2.98 | Short |
30 | [d-Dab(CO-NH-OCH3)3, 4Aph(CO-NH-OCH3)5,d-4Aph(CO-NH-OCH3)6]degarelix | 98 | 98 | 28.9 | 1619.6 | 1619.8 | 8.83 ± 0.04 | 1.49 | Short |
31 | [4Aph(CO-NH-OCH3)5,d-4Aph(CO-NH-OCH3)6,Orn(IGly)8]degarelix | 99 | 99 | 30.9 | 1637.8 | 1637.7 | 8.82 ± 0.20 | 1.53 | Short |
Percentage purity determined by HPLC using buffer system A; TEAP, pH 2.30, buffer system B, 60% CH3CN/40% A under gradient conditions (30% to 80% B over 50 min), at flow rate of 0.2 mL/min on a Vydac C18 column (0.21 × 15 cm, 5 μm particle size, 300 Å pore size). Detection at 214 nm.
Percentage purity determined by capillary zone electrophoresis (CZE ) using a Beckman P/ACE System 2050 controlled by an IBM Personal system/2 model 50Z; field strength of 15 kV at 30 °C. Buffer, 100 mM sodium phosphate (85:15, H2O:CH3CN), pH 2.50, on a Agilent μSil bare fused-silica capillary (75 μm i.d. × 40 cm length). Detection at 214 nm.
Retention times under gradient conditions (30% to 80% B over 50 min); buffer system A; TEAP, pH 7.0, buffer system B, 60% CH3CN/40% A.
Mass spectra (MALDI-MS) were measured on an ABI-Voyager DESTR instrument using saturated solution of α-cyano-4-hydroxycinnamic acid in 0.3% trifluoroacetic acid and 50% acetonitrile as matrix. The calculated [M + H]+of the monoisotope compared with the observed [M + H]+ monoisotopic mass.
The pIC50 is the negative log of the IC50 in Molar, as determined in the GnRH reporter gene assay.
IC50 is the concentration of antagonist required to repress the GnRH induced response by 50% in the reporter gene assay in HEK-293 cells expressing the human GnRH receptor and a GnRH-responsive stably integrated luciferase reporter gene.
Castrated male rat assay. Duration of action: very long = over 80% inhibition of LH release for more than 120 h;
*long = over 80% inhibition of LH release at 96 h but not at 120 h; long = over 80% inhibition of LH release at 72 h but not at 96 h; short = over 80% inhibition of LH release at 3 h but not at 72 h; ND = not determined.