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CAS No. : | 188968-51-6 | MDL No. : | MFCD04307743 |
Formula : | C27H40N8O7 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | AMLYAMJWYAIXIA-VWNVYAMZSA-N |
M.W : | 588.66 | Pubchem ID : | 176873 |
Synonyms : |
EMD 121974;EMD-85189;NSC-?707544;EMD-12192
|
Chemical Name : | 2-((2S,5R,8S,11S)-5-Benzyl-11-(3-guanidinopropyl)-8-isopropyl-7-methyl-3,6,9,12,15-pentaoxo-1,4,7,10,13-pentaazacyclopentadecan-2-yl)acetic acid |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water; | 80 mg of cyclo-(Arg-Gly-Asp-DPhe-NMeVal) (SEQ ID NO 11) are dissolved in 0.01 M MeSO3H (methane sulfonic acid) five to six times and freeze dried after each dissolving operation. Subsequent purification by HPLC give cyclo-(Arg-Gly-Asp-DPhe-NMeVal) (SEQ ID NO 11).x.MeSO3H; RT=17.8; FAB-MS (M+H): 589. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; In water; | 80 mg of cyclo-(Arg-Gly-Asp-DPhe-NMeVal) (SEQ ID NO 11) are dissolved in 0.01 M HCl five to six times and freeze dried after each dissolving operation. Subsequent purification by HPLC give cyclo-(Arg-Gly-Asp-DPhe-NMeVal) (SEQ ID NO 11).x.HCl; FAB-MS (M+H): 589. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water;vacuum evaporation; | TFA salt is removed from the above-produced cyclic peptide by suspending the cyclo-(Arg-Gly-Asp-DPhe-NMeVal) (SEQ ID NO 11).x.TFA in water followed by evaporation under vacuum to remove the TFA. The cyclic peptide formed is referred to as an "inner salt" and is designated cyclo-(Arg-Gly-Asp-DPhe-NMeVal) (SEQ ID NO 11). The term "inner salt" is used because the cyclic peptide contains two oppositely charged residues which intra-electronically counterbalance each other to form an overall noncharged molecule. One of the charged residues contains an acid moiety and the other charged residue contains an amino moiety. When the acid moiety and the amino moiety are in close proximity to one another, the acid moiety can be deprotonated by the amino moiety which forms a carboxylate/ammonium salt species with an overall neutral charge. | |
With ammonium hydroxide; In water; at 20℃;pH 6.8; | Example 19 Crystallization of the Inner Salt from the Trifluoroacetate (0900) 1.41 g cyclo-(Arg-Gly-Asp-DPhe-NMeVal)×TFA are dissolved in 10 ml water. By use of conc. aqueous ammonia pH is adjusted to ?6.8. After standing over night at ambient temperature, crystals appear, which are separated by filtration, washed with ice-cold water, and dried on air. Mother liquor is concentrated to yield addition crystalline product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
8.Procedure to Obtain Crystalline Form S2 Including Crystallization from Ethanol/Water MixturesCyclo-(Arg-Gly-Asp-DPhe-NMeVal)*TFA*H2SO4 (400 g) is dissolved in water (1600 ml) at 59° C.The pH is adjusted to pH=6.8 by addition of aqueous ammonia (30percent).Methanol (9600 ml) is added to the solution over a period of 3 h.The obtained mixture is cooled to 23° C. within 3 h and stirred at this temperature over night.Then, the mixture is cooled to 5° C. and stirred another 2 h.The precipitated raw product is isolated by sucction filtration and washed with cold methanol.Drying under vacuum for 48 h at 50° C. yields 335 g of Cilengitide (crystalline form S2, HPLC: 99.8percent).The raw material (335 g) is dissolved in water (1507 g) at 58° C. Methanol (8040 ml) is added to the solution over a period of 3 h.The thus formed suspension is then cooled to 23° C. within 3 h and stirred at this temperature over night.The suspension is then cooled to 5° C. and stirred for another 3 h.The product is isolated by sucction filtration and washed with methanol. | ||
Drying under vaccuum for 48 h at 60° C. yields 309 g of Cilengitide (crystalline form S1, HPLC: 99.9percent, 3.8percent MeOH, IC: <0.1percent Cl-, 0.0007percent TFA and 10.3percent SO42-).The 150 g of the above obtained material are dissolved in water (600 ml) and ethanol (600 ml) at 56° C.The mixture is cooled to 23° C. within 3 h and stirred over night.The mixture (suspension) is cooled to 5° C. and stirred for 2 h at this temperature.The product is isolated by sucction filtration and washed with cold water.Drying under vaccuum for 48 h at 60° C. yields 115.4 g of Cilengitide (crystalline form S2, ?0.05percent Methanol, 5.3percent EtOH IC: <0.01percent Cl-, <0.0011percent TFA, 0.34percent SO42-). | ||
Cilengitide.The cilengitide was prepared according to the method described in Dechantsreiter MA et al. (J Med Chem 1999, 42:3033-3040).1H-NMR (500 MHz, H2O:D2O-d2 9:1, 298 K): delta = 8.55 (d, J = 8.06 Hz, NH Asp), 8.37 (d, J = 7.28 Hz, NH Arg), 8.13 ( d, J = 9.19 Hz, NH Phe), 7.97 (m, NH Gly), 7.34 (m, 2H, C6H5 Phe), 7.26 (m, 3H, C6H5 Phe), 7.22 (t, J = 5.53/5.53 Hz, NHepsilon Arg), 5.19 (dd, J = 8.58/16.02 Hz, CHalpha Phe), 4.56 (dd, J = 7.45/- Hz, CHalpha Asp), 4.34 (d, J = 10.89 Hz, CHalpha MeVal), 4.12 (dd, J = 7.80/14.63 Hz, CH Gly), 3.95 (dd, J = 6.84/15.33 Hz, CHalpha Arg), 3.54 (dd, J = 3.37/14.60 Hz, CH Gly), 3.20 (m, CH2delta Arg), 3.02 (m, CH2beta Phe), 2.88 (s, CH3 MeVal), 2.84 (dd, J = 7.26/16.68 Hz, CHbeta Asp), 2.63 (dd, J = 7.60/16.54 Hz, CHbeta Asp), 2.06 (m, CHbeta Val), 1.91 (m, CH2beta Arg), 1.57 (m, CH2gamma Asp), 0.88 (d, J = 6.55 Hz, CH3 Val1), 0.56 (d, J = 6.49 Hz, CH3 Val2). |
With diphenylphosphoranyl azide; sodium hydrogencarbonate; In dichloromethane; N,N-dimethyl-formamide; at 20℃; for 16.0h; | General procedure: 10589] A solution of 0.6 g of R-NMe-Arg(Mtr)-Gly-Asp (OBut)-D-Phe-Val-ONa [obtainable for example from FmocNMe-Arg(Mtr)-Gly-Asp(OBut)-D-Phe-Val-0-Wang,-0-Wang being the radical of a 4-hydroxymethyl-phenoxym- ethyl -polystyrene resin used in the modified Merrifield techniques, by removal of the Fmoc group with piperidine/DMF and elimination of the resin with TFACR2C12 (1:1)] in 15 ml of DMF is diluted with 85 ml of dichloromethane, and 50mg of NaRCO3 are added. Afier cooling in a dry ice/acetone mixture, 40 III of diphenylphosphoryl azide are added. After standing at room temperature for 16 hours, the solution is concentrated. The concentrate is gel-filtered (Sephadex 010 column in isopropanol/water 8:2) and then purified by RPLC in the customary mannet Treatment with TFAR2 0 (98:2) gives cyclo-(NMe-Arg-Gly-Asp-D-Phe-Val) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; In water; | 10595] 80 mg of cyclo-(Arg-Gly-Asp-DPhe-NMeVa1) are dissolved in 0.01 m RC1 five to six times and freeze-dried afier each dissolving operation. Subsequent purification by RPLC gives cyclo-(Arg-Gly-Asp-DPhe-NMeVa1) x RC1; FAR-MS (M+R): 589. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With methanesulfonic acid; | 10595] 80 mg of cyclo-(Arg-Gly-Asp-DPhe-NMeVa1) are dissolved in 0.01 m RC1 five to six times and freeze-dried afier each dissolving operation. Subsequent purification by RPLC gives cyclo-(Arg-Gly-Asp-DPhe-NMeVa1) x RC1; FAR-MS (M+R): 589:_Analogously the following is obtained by the treatment with methane sulfonic acid (MeSO3R):from cyclo-(Arg-Gly-Asp-DPhe-NMeVa1): cyclo-(Arg-GlyAsp-DPhe-NMeVa1) x MeSO3R; RT=17,8; FAB-MS(M+R):589; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ammonium hydroxide; In water; at 4℃;pH 6.8; | Example 18 Crystallization of the Inner Salt from the Hydrochloride (0899) 1.25 g of cyclo-(Arg-Gly-Asp-DPhe-NMeVal) x HCl are dissolved in 10 ml water. By use of conc. aqueous ammonia pH is adjusted to ?6.8. After standing over night at 4 C, crystals appear, which are separated by filtration, washed with ice-cold water, and dried on air. Mother liquor is concentrated to yield additional crystalline product |