Peptide derivatives

Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Peptide containing doai

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530330, 514 17, C07K 500, C07K 700, A61K 3800

Patent

active

058406999

DESCRIPTION:

BRIEF SUMMARY
This application is a 371 of PCT/JP96/00949 filed Apr. 8, 1996.


TECHNICAL FIELD

This invention relates to novel peptide derivatives having an antitumor activity and, more particularly, to peptide derivatives of the formula ##STR3## or salts thereof, wherein: (a) Q.sub.1 represents a 1-dimethylamino-2-methylpropyl group and Q.sub.2 represents an (R)- or (S)-2-hydroxy-2-phenylethylamino group, a 2-phenylcyclopropylamino group or a 1,2,3,4-tetrahydroisoquinolin-2-yl group, or represents ##STR4## where A represents a hydrogen atom or ##STR5## in which Y represents a hydrogen atom or --COR.sub.1, and R.sub.1 represents a hydroxyl group, a lower alkoxy group, an aralkyloxy group or ##STR6## in which R.sub.2 and R.sub.3 may be the same or different and each represents a hydrogen atom, a lower alkyl group, a phenyl group, or a four- to seven-membered heterocyclic group containing one or two heteroatoms selected from S, O and N, or R.sub.2 and R.sub.3, together with the nitrogen atom to which they are attached, may form a four- to seven-membered heterocyclic group which may further contain one heteroatom selected from S, O and N, and halogen atom, hydroxyl group, lower alkyl group or lower alkoxy group.


BACKGROUND ART

Up to now, several compounds having a cell growth inhibiting activity and/or an antineoplastic activity have been isolated from a marine mollusk (Dolabella auricularia) which is akin to the sea hare, and these compounds are called dolastatins 1-15. Among them, dolastatin 10 is a pentapeptide extracted from the Indian Ocean (sea hare Dolabella auricularia) by Pettit in 1987 and having the structural formula given below, and is known to be a compound having the most powerful cell growth inhibiting activity of all the existing compounds (see Pettit et al., Journal of the American Chemical Society, Vol. 109, p. 6883, 1987 and U.S. Pat. No. 4,816,444). ##STR7##
Thereafter, the total synthesis of dolastatin 10 was also reported (see U.S. Pat. No. 4,978,744).
Meanwhile, the present inventors previously disclosed certain derivatives of dolastatin 10 (see the pamphlets of WO 93/03054 and WO 95/09864).
Now, the present inventors have found that (a) certain derivatives of dolastatin 10 obtained by replacing the dolaphenine 10 by another substituent group and (b) certain derivatives of dolastatin 10 obtained by replacing the dolavaline (N,N-dimethylvaline) located at the N-terminus of dolastatin 10 by N-methylproline have a far more powerful antitumor activity than dolastatin 10.


DISCLOSURE OF THE INVENTION

The term "lower" as used herein means that the groups or compounds modified by this term have not more than six carbon atoms and preferably not more than four carbon atoms.
In the above formula (I), examples of the "lower alkyl group" include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and n-hexyl groups, and examples of the "lower alkoxy group" include methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy groups. Moreover, the "aralkyloxy group" means an aryl-(lower alkyl)oxy group, and examples thereof include benzyloxy and phenetyloxy. The "halogen atoms" include fluorine, chlorine, bromine and iodine atoms.
When R.sub.2 or R.sub.3 represents "a four- to seven-membered heterocyclic group containing one or two heteroatoms selected from S, O and N," examples of the heterocyclic group include azetidinyl, furyl, thienyl, pyridyl, piperidinyl, azepinyl, thiazolyl, imidazolyl, oxazolyl, pyrimidinyl and pyridazinyl groups. On the other hand, when R.sub.2 and R.sub.3, together with the nitrogen atom to which they are attached, form a four- to seven-membered heterocyclic group which may further contain one heteroatom selected from S, O and N," examples of the heterocyclic group include azetidino, pyrrolidino, piperidino, 1-perhydroazepinyl, piperazino, morpholino, and thiomorpholino groups.
Thus, examples of the group ##STR8## include amino, methylamino, ethylamino, isopropylamino, tert-butylamino, dimethylamino, diethylamino, phenylamino, N-methyl-N-phenylamino, furylamino, p

REFERENCES:
patent: 4816444 (1989-03-01), Pettit et al.
patent: 4978744 (1990-12-01), Pettit et al.
patent: 5635483 (1997-06-01), Pettit et al.
patent: 5654399 (1997-08-01), Sakakibara et al.
patent: 5741892 (1998-04-01), Barlozzari et al.
Pettit et al., "The Isolation and Structure of a Remarkable Marine Animal Antineoplastic Constituent: Dolastatin 10", J. Am. Chem. Soc. 1987, 109, 6883-6885.

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