916
Dannecker-Dörig, Linden, Heimgartner:
(3s, 3 arom . C); 132.2, 130.6, 129.8, 129.5, 129.4, 129.1, 128.5, 128.3, 128.2 (9d, 15 arom .
CH); 68.1 (t, Ph CH2O); 61.2 (s, C(2)(Ph e(2Me))); 58.8, 58.5 (2s, 2 C(2)(Aib)); 45.7 (t,
CH2(Gly)); 41.7 (t, Ph CH2); 41.3 (q, MeN); 27.0, 26.7, 26.5, 25.2, 23.8 (5q, 2 Me2C, MeC(2)).
CI-MS: 523 (100, [M + 1 – Ph (Me)N]+). For C35H43N5O6 (629.76) calculated: 66.75% C,
6.88% H, 11.12% N; foun d: 66.63% C, 7.12% H, 11.06% N.
Z-Gly-Phe(2Me)-Aib-Aib-OH (17). 11.44 g (18.2 m m ol) of 16 were dissolved in THF/6 M HCl
(1:1, 182 m l) an d th e solution was stirred at r.t. for 6 h . Th e workup as for com poun d 15
gave 8.6 g (87%) of 17; colorless solid; m .p. 138.5 °C. IR (KBr): 3310m (br), 1730m (br),
1665s (br), 1530s (br), 1455m , 1280m , 1235m , 1160m . 1H NMR (400 MHz, aceton e-d6):
10.52 (br s, COOH); 7.59, 7.53, 7.44 (3s, 3 NH); 7.40–7.10 (3m , 10 arom . H); 6.95 (X part of
ABX, J = 5.0, NH(Gly)); 5.13, 5.04 (AB, J = 12.5, Ph CH2O); 3.81, 3.80 (AB of ABX, J = 16.5,
5.5, CH2(Gly)); 3.37, 3.05 (AB, J = 13.5, Ph CH2); 1.48, 1.38 (2s, 2 Me2C); 1.30 (s, MeC(2)).
13C NMR (50.4 MHz, aceton e-d6): 175.8, 174.9, 174.4, 171.7 (4s, COOH, 3 CO(am ide));
158.3 (s, CO(ureth an e)); 137.9, 137.4 (2s, 2 arom . C); 131.6, 129.2, 128.9, 128.7, 128.6,
127.4 (6d, 10 arom . CH); 67.3 (t, Ph CH2O); 60.5 (s, C(2)(Ph e(2Me))); 57.4, 57.0 (2s,
2 C(2)(Aib)); 45.6 (t, CH2(Gly)); 40.8 (t, Ph CH2); 26.3, 25.5, 25.4, 24.5, 23.4 (5q, 2 Me2C,
MeC(2)). CI-MS: 541 (42, [M + 1]+), 523 (100, [M + 1 – H2O]+). For C28H36N4O7 (540.62) cal-
culated: 62.21% C, 6.71% H, 10.36% N; foun d: 62.20% C, 6.58% H, 10.19% N.
Z-Gly-Phe(2Me)-Aib-Aib-Aib-NMe2 (18). To a solution of 17 (9.68 g, 17.9 m m ol) in THF (40 m l)
an d DMF (8 m l) at 0 °C was added dropwise 3-(dim eth ylam in o)-2,2-dim eth yl-2H-azirin e (2c;
2.35 g, 20.9 m m ol). Th en , th e m ixture was stirred at 0 °C for 15 h . Th e workup as for com -
poun d 14 gave 11.52 g (99%) of 18; colorless solid; m .p. 203–212 °C. IR (KBr): 3320m ,
3280m , 1705m , 1685s, 1655s, 1625s, 1550m , 1525m , 1270m . 1H NMR (400 MHz, DMSO-d6):
8.23, 7.87, 7.44 (3s, 3 NH); 7.57 (t, J = 6.0, NH(Gly)); 7.40–7.00 (2m , 10 arom . H, NH); 5.06,
4.99 (AB, J = 12.6, Ph CH2O); 3.80–3.50 (2m , CH2(Gly)); 3.31 (s, Me2N); 3.29, 2.96 (AB, J =
13.3, Ph CH2); 1.34, 1.33, 1.32, 1.30, 1.28 (5s, 3 Me2C); 1.19 (s, MeC(2)). 13C NMR (50.4 MHz,
DMSO-d6): 176.6, 173.7, 173.3, 172.2, 170.6 (5s, 5 CO(am ide)); 156.9 (s, CO(ureth an e));
137.1, 136.9 (2s, 2 arom . C); 131.0, 128.5, 128.04, 128.00, 127.7, 126.5 (6d, 10 arom . CH);
65.7 (t, Ph CH2O); 58.9 (s, C(2)(Ph e(2Me))); 56.4, 56.2, 55.7 (3s, 3 C(2)(Aib)); 43.8 (t,
CH2(Gly)); 39.1 (t, Ph CH2); 37.4 (br q, Me2N); 26.8, 26.1, 25.7, 24.0, 23.6, 22.5 (6q, 3 Me2C,
MeC(2)). EI-MS: 608 (100, [M – 45]+), 523 (26), 518 (12), 474 (11), 438 (24), 185 (14), 134
(70), 93 (31), 91 (75). For C34H48N6O7 (652.80) calculated: 62.56% C, 7.41% H, 12.87% N;
foun d: 62.37% C, 7.21% H, 12.78% N.
Z-Gly-Phe(2Me)-Aib-Aib-Aib-OH (19). 1.68 g (2.35 m m ol) of 18 were dissolved in THF/6 M HCl
(1:1, 182 m l) an d th e solution was stirred at r.t. for 6 h . After th is tim e, th e reaction was n ot
com plete. Th e workup as for com poun d 15 gave 0.92 m g (63%) of 19. Th e an alogous h ydro-
lysis of 200 m g (0.31 m m ol) of 18 un der reflux (16 h ) gave 168 m g (88%) of 19; colorless
solid; m .p. 223–225 °C. IR (KBr): 3350m , 3310m , 1725m , 1680m , 1670m , 1650s, 1565m ,
1555m , 1455w, 1280w, 1255w, 1150w. 1H NMR (400 MHz, DMSO-d6): 11.13 (br s, COOH);
7.60–7.45 (m , NH); 7.42, 7.38 (2s, 2 NH); 7.30–7.00 (m , 10 arom . H); 5.02, 4.91 (AB, J =
12.3, Ph CH2O); 3.75–3.50 (m , CH2(Gly)); 3.26, 2.90 (AB, J = 13.0, Ph CH2); 1.43, 1.37, 1.36,
1.31 (4s, 3 Me2C); 1.23 (s, MeC(2)). 13C NMR (50.4 MHz, DMSO-d6): 178.0 (s, COOH); 176.6,
176.3, 176.0, 172.4 (4s, 4 CO(am ide)); 159.3 (s, CO(ureth an e)); 138.4, 138.0 (2s, 2 arom . C);
132.2, 129.9, 129.5, 129.4, 129.1, 128.1 (6d, 10 arom . CH); 67.9 (t, Ph CH2O); 60.8 (s,
C(2)(Ph e(2Me))); 58.1, 58.0, 57.1 (3s, 3 C(2)(Aib)); 45.6 (t, Ph CH2); 41.3 (t, CH2(Gly)); 27.1,
26.8, 26.2, 25.3, 25.1, 24.8, 23.9 (7q, 3 Me2C, MeC(2)). A doublin g of th e sign als at 176.6,
176.3, an d 58.0 was observed, wh ich disappeared at 60 °C. CI-MS: 626 (25, [M + 1]+), 608
Collect. Czech. Chem. Commun. 2009, Vol. 74, No. 6, pp. 901–925